Surfactant-compatible star macromolecules

ABSTRACT

The present invention relates to multi-arm surfactant-system thickening star macromolecules, and methods of preparing and using the same. In one aspect of the invention, a surfactant-system thickening star macromolecule is capable of providing surfactant-compatibility, increase the viscosity of a surfactant-containing system, and/or temperature-stability to an aqueous composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority from U.S. ProvisionalApplication No. 62/020,736, filed Jul. 3, 2014. The foregoing relatedapplication, in its entirety, is incorporated herein by reference.

This application is further related to U.S. patent application Ser. No.12/926,143, filed on Oct. 27, 2010, which is now U.S. Pat. No.8,173,750, which is a continuation-in-part of U.S. patent applicationSer. No. 12/799,411, filed on Apr. 23, 2010, which claims priority toU.S. Application No. 61/214,397, filed on Apr. 23, 2009, each of theseapplications are incorporated herein by reference in their entirety.This application is further related to U.S. patent application Ser. No.12/926,780, filed on Dec. 8, 2010, which is a continuation-in-part ofU.S. patent application Ser. No. 12/653,937, filed on Dec. 18, 2009,which claims priority to U.S. Application No. 61/203,387, filed on Dec.22, 2008, each of these applications are incorporated herein byreference in their entirety. This application is further related to U.S.Application No. 61/695,103, filed on Aug. 30, 2012, which isincorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates to preparation of surfactant-systemthickening star macromolecules, and methods of using the same as agentsproviding surfactant compatibility and temperature stability assurfactant-system thickening agents, or as rheology modifiers.

SUMMARY OF THE INVENTION

An aspect of the invention provides a surfactant-system thickeningmacromolecule that is suitable for increasing the viscosity of asurfactant-containing system, wherein the surfactant-system thickeningmacromolecule comprises:

-   -   a) a core;    -   b) at least one first polymeric arm, comprising a hydrophilic        polymeric segment covalently attached to the core; and    -   c) at least one second polymeric arm, comprising:        -   i) a hydrophilic polymeric segment covalently attached to            the core; and        -   ii) a further segment covalently attached to the hydrophilic            polymeric segment, wherein the further segment is comprised            of at least one monomeric residue of a polymerized            surfactant-system thickening monomer comprising a C₆ or            greater alkyl acrylate; C₆ or greater alkenyl acrylate; C₆            or greater alkyl alkyl acrylate; C₆ or greater alkenyl alkyl            acrylate; C₆ or greater alkyl acrylamide; C₆ or greater            alkenyl acrylamide; C₆ or greater alkyl alkyl acrylamide; C₆            or greater alkenyl alkyl acrylamide; C₂ or greater alkyl            vinyl ether, C₂ or greater alkenyl vinyl ether, C₁ or            greater alkyl allyl ether, or C₁ or greater alkenyl allyl            ether.

In another aspect of the invention, the surfactant-system thickeningmacromolecule may be represented by Formula A:

[(P1)_(q1)]_(r)-Core-[(P3)_(q3)-(P2)_(q2)]_(s)  Formula A

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents a polymeric segment of a first        polymeric arm comprised of monomeric residues of polymerized        hydrophilic monomers;    -   P2 independently represents a further segment of a second        polymeric arm comprised of at least one monomeric residue of a        polymerized surfactant-system thickening monomer;    -   P3 independently represents a polymeric segment of the second        polymeric arm comprised of monomeric residues of polymerized        hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   r independently represents the number of the first polymeric        arms covalently attached to the Core; and    -   s independently represents the number of the second polymeric        arms covalently attached to the Core.

In another aspect of the invention, the surfactant-system thickeningmacromolecule may be represented by Formula B:

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents a polymeric segment of a first        polymeric arm comprised of monomeric residues of polymerized        hydrophilic monomers;    -   P2 independently represents a further segment of a second        polymeric arm comprised of at least one monomeric residue of a        polymerized surfactant-system thickening monomer;    -   P3 independently represents a polymeric segment of the second        polymeric arm comprised of monomeric residues of polymerized        hydrophilic monomers;    -   P4 independently represents a polymeric segment of a third        polymeric arm comprised of monomeric residues of polymerized        hydrophobic monomers;    -   P5 independently represents a polymeric segment of the third        polymeric arm comprised of monomeric residues of polymerized        hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   q4 independently represents the number of monomeric residues in        P4;    -   q5 independently represents the number of monomeric residues in        P5;    -   r independently represents the number of the first polymeric        arms covalently attached to the Core;    -   s independently represents the number of the second polymeric        arms covalently attached to the Core; and    -   t independently represents the number of the third polymeric        arms covalently attached to the Core.

In another aspect of the invention, a surfactant-modified starmacromolecule is provided that may comprise:

-   -   i) a core;    -   ii) at least one first polymeric arm, comprising a hydrophilic        polymeric segment covalently attached to the core; and    -   iii) at least one second polymeric arm, comprising:        -   a) a hydrophilic polymeric segment covalently attached to            the core; and        -   b) a further segment comprising at least one pendant moiety            represented by [L¹-G¹-L²-G²];            wherein:    -   G¹ independently represents a residue of a hydrophilic moiety of        the surfactant;    -   G² independently represents a residue of a hydrophobic moiety of        the surfactant;    -   L¹ independently represents a linking group or a covalent bond,        attaching G¹ to the further segment; and    -   L² independently represents a linking group or a covalent bond,        linking G¹ and G².

In another aspect of the invention, a method of increasing the viscosityof a surfactant-containing aqueous system may comprise introducing asurfactant-system thickening macromolecule into thesurfactant-containing aqueous system, wherein the surfactant-systemthickening macromolecule may be represented by Formula C:

[(P1)_(q1)]_(r)-Core-[(P3)_(q3)-(P2)_(q2)],  Formula C

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents a polymeric segment of the at least        one first polymeric arm comprised of monomeric residues of        polymerized hydrophilic monomers;    -   P2 independently represents a further segment of the at least        one second polymeric arm comprised of:        -   1) a polymerized backbone comprising at least one pendant            micelle-philic moiety, or        -   2) at least one monomeric residue of a polymerized            micelle-philic monomer,    -   P3 independently represents a polymeric segment of the at least        one second polymeric arm comprised of monomeric residues of        polymerized hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   r independently represents the number of the at least one first        polymeric arms covalently attached to the Core; and    -   s independently represents the number of the at least one second        polymeric arms covalently attached to the Core.

In another aspect of the invention, a method of increasing the viscosityof a surfactant-containing aqueous system may comprise introducing asurfactant-system thickening macromolecule into thesurfactant-containing aqueous system, wherein the surfactant-systemthickening macromolecule may be represented by Formula D:

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents a polymeric segment of the at least        one first polymeric arm comprised of monomeric residues of        polymerized hydrophilic monomers;    -   P2 independently represents a further segment of the at least        one second polymeric arm comprised of:        -   1) a polymerized backbone comprising at least one pendant            micelle-philic moiety, or        -   2) at least one monomeric residue of a polymerized            micelle-philic monomer,    -   P3 independently represents a polymeric segment of the at least        one second polymeric arm comprised of monomeric residues of        polymerized hydrophilic monomers;    -   P4 independently represents a polymeric segment of the at least        one third polymeric arm comprised of monomeric residues of        polymerized hydrophobic monomers;    -   P5 independently represents a polymeric segment of the at least        one third polymeric arm comprised of monomeric residues of        polymerized hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   q4 independently represents the number of monomeric residues in        P4;    -   q5 independently represents the number of monomeric residues in        P5;    -   r independently represents the number of the at least one first        polymeric arms covalently attached to the Core;    -   s independently represents the number of the at least one second        polymeric arms covalently attached to the Core; and    -   t independently represents the number of the at least one third        polymeric arms covalently attached to the Core.

In another aspect of the invention, a method of increasing the viscosityof a surfactant-containing aqueous system may comprise introducing asurfactant-system thickening macromolecule into thesurfactant-containing aqueous system, wherein the surfactant-systemthickening macromolecule may comprise:

-   -   a) a core;    -   b) at least one first polymeric arm, comprising a hydrophilic        polymeric segment covalently attached to the core; and    -   c) at least one second polymeric arm, comprising:        -   i) a hydrophilic polymeric segment covalently attached to            the core; and        -   ii) a further segment covalently attached to the hydrophilic            polymeric segment, wherein the further segment is comprised            of at least one monomeric residue of a polymerized            surfactant-system thickening monomer comprising a C₆ or            greater alkyl acrylate; C₆ or greater alkenyl acrylate; C₆            or greater alkyl alkyl acrylate; C₆ or greater alkenyl alkyl            acrylate; C₆ or greater alkyl acrylamide; C₆ or greater            alkenyl acrylamide; C₆ or greater alkyl alkyl acrylamide; C₆            or greater alkenyl alkyl acrylamide; C₂ or greater alkyl            vinyl ether, C₂ or greater alkenyl vinyl ether, C₁ or            greater alkyl allyl ether, or C₁ or greater alkenyl allyl            ether.

In another aspect of the invention, a method of increasing the viscosityof a surfactant-containing aqueous system may comprise introducing asurfactant-modified star macromolecule into the surfactant-containingaqueous system, wherein the surfactant-modified star macromolecule maycomprise:

-   -   i) a core;    -   ii) at least one first polymeric arm, comprising a hydrophilic        polymeric segment covalently attached to the core; and    -   iii) at least one second polymeric arm, comprising:        -   a) a hydrophilic polymeric segment covalently attached to            the core; and        -   b) a further segment comprising at least one pendant moiety            represented by [L¹-G¹-L²-G²];            wherein:    -   G¹ independently represents a residue of a hydrophilic moiety of        the surfactant;    -   G² independently represents a residue of a hydrophobic moiety of        the surfactant;    -   L¹ independently represents a linking group or a covalent bond,        attaching G¹ to the further segment; and    -   L² independently represents a linking group or a covalent bond,        linking G¹ and G².

In another aspect the invention, a polymer composition comprising starmacromolecules is provided, each star macromolecule having a core andfive or more arms, wherein the number of arms within a starmacromolecule varies across the composition of star molecules; and thearms on a star are covalently attached to the core of the star; each armcomprises one or more (co)polymer segments; and at least one arm and/orat least one segment exhibits a different solubility from at least oneother arm or one other segment, respectively, in a reference liquid ofinterest.

In another aspect of the invention, the star macromolecule may besuitable for providing surfactant compatibility, surfactant-systemthickening, an increase in viscosity of a surfactant-containing system,such as an increase in viscosity of a surfactant-containing aqueoussystem, use as thickening agents, use as rheology modifiers, use inhydraulic fracturing fluids, use in oil and gas applications, use inmining applications, use in cosmetic and personal care applications, usein home care applications, use in paint and printing, use in adhesiveapplications, use in electronic applications, use in medical andpharmaceutical applications, use in paper applications, or use inagricultural applications.

In another aspect of the invention, the star macromolecule may provide,or may be used to provide, a certain level of control over viscosity, anincrease in viscosity of a system, and consistency factors in manyaqueous and oil based systems, including, for example, hydraulicfracturing fluid additives, gelling agents, gels, proppant stabilizers,breakers, friction reducers, and thickening agents.

In another aspect of the invention, the star macromolecule, includingthose formed by a one-pot process, ATRP, CRP, and/or combinations of oneor more of these processes, may be an emulsifier, may form a gel, mayform an emulsifier-free emulsion, may be an emulsion and/or thickeningagent.

In another aspect of the invention, the star macromolecules may besuitable in oil and gas applications, including but not limited to, asrheology modifiers for fracturing fluids/drilling well fluids, gellingagents, gels, dispersants, proppant stabilizers and carriers, breakers,friction reducers, lubricants, scale-buildup inhibitors, heat transferfluids, thickening agents, additives to improve oil extraction from oilsands, emulsion breakers for oil-sand-water emulsions, additives toimprove dewatering of oil sands, gasoline additives, gasolinestabilizers, coiled tubing clean out fluids, drilling fluids, completionfluids, stimulation fluids, production fluids, hydraulic fracturingfluids, injection fluids, flooding fluids, flow assurance fluids,hydrate inhibitors, asphaltene inhibitors, asphaltenes inhibitors, scaleinhibitors, paraffin inhibitors, friction reducers, corrosioninhibitors, H₂S scavengers, de-emulsifiers, foam controlling agents,de-foaming agents, lubricants, scale removers, asphaltene removers, dragreducers, pour point depressants, cold flow improvers, traceablechemicals, foaming agents, viscoelasctic surfactants, and/orviscoelastic surfactant fluid additives.

In another aspect of the invention, the star macromolecules may besuitable in mining applications, including but not limited to,concentration of grinding circuit; leach; concentrate tailings; CounterCurrent Decantation (CCD); paste backfill; clarification; dustsuppressants; flocculating agents; carbon powder recycling; coal,diamond, gold and precious metal extraction and processing; lubricantsand drag reduction agents for pipeline slurry transport; flocculants;scale inhibitors; frothers; defoamers; dewatering agents; crystal growthmodifiers; filtration aids; dust control agent; dispersant; depressant;thickener; clarifier, solvent extraction reagent; antiscalant aid;and/or smoothing aid.

In another aspect of the invention, the star macromolecules may besuitable in cosmetic and personal care applications, including but notlimited to, cosmetic creams, lotions, gels, sprayable lotion, sprayablecream, sprayable gel, hair styling agents, hair styling sprays andmousses, mouse, hair conditioners, shampoos, bath and showerpreparations, shower gel, hair gel, hair care product, ointments,deodorants and antiperspirants, anti-persperant ingredient, deodorantingredient, mascara, blush, lip stick, eye liner, perfumes, powders,serums, skin sensoric, skin cleansers, skin conditioners, emollient,skin emollients, skin moisturizers, moisturizer, skin wipes, sensorymodifier, skin care product, make-up remover, eye cream, leave-onproduct, wash off product, products for care of the teeth and the mouth,whitening products, mouthwash, products for external intimate hygiene,sunscreens, products for tanning without sun, shaving preparations,shaving cream, depilatories, products removing make-up, products forexternal intimate hygiene, spermicides, condom lubricant, personalhygiene lubricant, solids, fabric softeners, cleansing product,cleansing spray, emulsifier, wetting agent, foamer, soap, soaps, liquidsoap, hand sanitizer, hand gel, conditioner, humectant, foam stabilizer,softener, clarifier, film former, delivery system, oil deliver system,active deliver system, rheology modifier, thickening agent, viscosifier,and lubricant.

In another aspect of the invention, the star macromolecules may besuitable in home care applications, including but not limited to,cleaners for windows and glass, and other household surfaces; cleanersfor toilet areas; hard surface cleaners; household cleaners; industrialcleaners; window cleaners; floor cleaners; shower cleaners; draincleaners; oven cleaners; tub, tile and sink cleaners; bleach; bleachcontaining cleaners; degreasers; enzyme production; liquid and gelledsoaps; polishes and waxes; car wax; floor wax; polishes; polish;detergents; liquid and powdered detergents, including detergents forlaundry and in dish washing; laundry detergents; laundry softeners; hardwater mineral removers; metal cleaner and polishes; carpet and rugcleaners; dusting products; upholstery cleaners; and floor careproducts.

In another aspect of the invention, the star macromolecules may besuitable in paint and printing applications, including but not limitedto, inkjet printer ink and other inks, 3-D printing fluid, 3-D printingink, pigments, wetting surfactants, binders, flocculants, dispersants,leveling compounds, antifoam, aerators, surface tension modifiers, filmformers, plasticizers, pore formers, water repellents, corrosioninhibitors, bittering agents to deter rodents.

In another aspect of the invention, the star macromolecules may besuitable in adhesive applications, including but not limited to,associative complexes, billboard adhesives, carpet backsizing compounds,hot melt adhesives, labeling adhesives, latex adhesives, leatherprocessing adhesives, plywood laminating adhesives, paper adhesives, 3-Dprinting adhesive, 3-D printing binder, wallpaper pastes, wood glue.

In another aspect of the invention, the star macromolecules may besuitable in electronic applications, including but not limited to,antistatic film and packaging, conductive inks, rheology control agentsused for copper foil production, multilayer ceramic chip capacitors,photoresists, plasma display screens, lubricants for wire, cable, andoptical fibers, gel lacquers for coil coating.

In another aspect of the invention, the star macromolecules may besuitable in medical and pharmaceutical applications, including but notlimited to, but not limited to, medical device lubrication,antibacterial coatings, pharmaceutical excipients such as binders,creams, ointments, liniments, pastes, diluents, fillers, lubricants,glidants, disintegrants, polish agents, suspending agents, dispersingagents, plasticizers.

In another aspect of the invention, the star macromolecules may besuitable in paper applications, including but not limited to, coatings,dispersion for tissue and thin papers, filler retention and drainageenhancement, flocculation and pitch control, grease-proof coatings,adhesives, release coatings, surface sizing, sizes for gloss and inkholdout, tail tie and pickup adhesives for papermaking, deinking ofrecycled papers in flotation, washing and enzymatic processes.

In another aspect of the invention, the star macromolecules may besuitable in agricultural applications, including but not limited to,animal feed, dispersing agents, drift control, encapsulation, seedcoatings, seed tape, spray adherents, water-based sprays and sprayemulsions, water-soluble packaging, herbicides, insecticides.

In another aspect of the invention, the star macromolecules may besuitable in other applications including but not limited to, water- andsolvent-based coating compositions, water- and solvent-based lubricants,water- and solvent-based viscosity index modifiers, paints,plasticizers, firefighting, anti-fogs agents, antifoaming agents,antifreeze substances, ski and snowboard waxes, laxatives, corrosioninhibitors, detergents, dental impression materials, dental fillers,ceramic and brick forming, prepolymers such as polyols for use inpolyesters, polyurethanes, polycarbonates. For rheology modifierapplications, characteristics are high gel strength, stability in thepresence of salt and increased temperatures, high shear thinningcharacteristics, forms versatile low viscosity soluble concentrations,and synergistic interactions with added agents to adjust their rheologyprofile to optimize properties such as sedimentation, flow and leveling,sagging, spattering, etc.

BRIEF DESCRIPTION OF THE FIGURES

The following figures exemplify aspects of the disclosed process but donot limit the scope of the process to the examples discussed.

FIG. 1. GPC curves of a macroinitiator, polymeric arms, and starmacromolecule from Example 1.

FIG. 2a . Viscosity vs. shear rate of aqueous solution of starmacromolecules prepared in Examples 1-4.

FIG. 2b . Expansion view of FIG. 2 a.

FIG. 3a . Comparison of viscosity vs. shear rate of aqueous solution ofdifferent polymers in surfactant system (6.4 wt. % of SLES).

FIG. 3b . Expansion view of FIG. 3 a.

FIG. 4. Dependence of the dynamic viscosity on the concentration of starmacromolecule (from Example 1) in surfactant system (6.4 wt. % of SLES).

FIG. 5. Dependence of the dynamic viscosity on the concentration ofsurfactant (SLES) for aqueous solution of star macromolecule (fromExample 1).

FIG. 6a . Viscosity vs. shear rate of aqueous solution with varyingamounts of star macromolecules in hybrid surfactants system (6.4 wt. %of SLES).

FIG. 6b . Expansion view of FIG. 6 a.

FIG. 7. Dependence of viscosity on temperature of aqueous solution ofstar macromolecules.

FIG. 8a . Comparison of viscosity vs. shear rate of aqueous solution ofdifferent polymers in hybrid surfactants system (6.4 wt. % of SLES, 2.5wt. % of CH).

FIG. 8b . Expansion view of FIG. 8 a.

FIG. 9. Dependence of the dynamic viscosity on the concentration of starmacromolecule (from Example 1) in surfactant system (6.4 wt. % of SLES,2.5 wt. % of CH).

FIG. 10. Dependence of the dynamic viscosity on the concentration ofsurfactant (SLES) for aqueous solution of star macromolecule (fromExample 1).

FIG. 11a . Comparison of viscosity vs. shear rate of aqueous solution ofdifferent polymers in hybrid surfactants system (6.4 wt. % of CB, 2.5wt. % of SLES).

FIG. 11b . Expansion view of FIG. 11 a.

FIG. 12a . Viscosity vs. shear rate of aqueous solution of starmacromolecule (from Example 1) in hybrid surfactants system (6.4 wt. %of CB, 2.5 wt. % of SLES).

FIG. 12b . Expansion view of FIG. 12 a.

FIG. 13. Dependence of the dynamic viscosity on pH for aqueous solutionsof star macromolecules in hybrid surfactants system (6.4 wt. % of CB,2.5 wt. % of SLES).

FIG. 14. Dependence of the dynamic viscosity on pH for aqueous solutionsof star macromolecule (from Example 1).

FIG. 15. Dependence of the dynamic viscosity on concentration of NaClfor aqueous solutions of star macromolecules in hybrid surfactantssystem (6.4 wt. % of CB, 2.5 wt. % of SLES).

FIG. 16. An images demonstrating phase separated water and sunflower oil(left) and the emulsifying properties of starmacromolecule (fromExample 1) (right).

DETAILED DESCRIPTION OF THE INVENTION

The term “solubility” or “soluble” is understood to mean that when acomponent is mixed into a solvent and tested, at STP in a 1 cm cuvette,it has a light transmittance value, at a wavelength at or around a UV/Vis minimum wavelength for the mixture, of at least 40%, for example, atleast 50%, 70%, 85%, or at least 95%.

The term “clear” as is used to describe a homogenous gel or homogenoussolution is understood to mean that when the gel or solution is tested,at STP in a 1 cm cuvette, it has a light transmittance value, at awavelength at or around a UV/V is minimum wavelength for the gel orsolution, of at least 40%, for example, at least 50%, 70%, 85%, or atleast 95%.

The term “water-soluble monomer” is understood to mean a monomer havingat least about 10 wt. % solubility in water at STP. For example, a watersoluble monomer may have at least 15 wt. %, 20 wt. %, 25 wt. %, or atleast 30 wt. % solubility in water at STP.

The term “water-insoluble monomer” is understood to mean a monomerhaving less water solubility than a water soluble monomer, for example,less that about 5 wt. %, such as less than 1 wt. % or 0.5 wt. %solubility in water at STP.

The term “water-soluble star macromolecule” is understood to mean a starmacromolecule that is soluble in water, pH adjusted if necessary to a pHof no greater than 8 with sodium hydroxide, at a concentration of atleast 5 g/L, for example, between 8 g/L to 100 g/L, such as, at least 10g/L, 12 g/L, 15 g/L, or at least 20 g/L. For example, a water-solublestar macromolecule having an aqueous solubility of at least 10 g/L mayinclude the introduction of at least 10 g of the star macromolecule intoapproximately 1 L of water, neutralizing the mixture, if necessary, byadjusting the pH of the resulting mixture to about pH 8 (e.g., with theaddition of base, such as sodium hydroxide), and vigorously stirring ata temperature no greater than 100° C. for no more than about 60 minutes,to achieve dissolution of the star macromolecule, and testing thesolubility at STP.

The term “oil-soluble star macromolecule” is understood to mean a starmacromolecule that is soluble in mineral oil at a concentration of atleast 5 g/L, for example, between 8 g/L to 100 g/L, such as, at least 10g/L, 12 g/L, 15 g/L, or at least 20 g/L of mineral oil. For example, anoil-soluble star macromolecule having an oil solubility of at least 10g/L may include the introduction of at least 10 g of the starmacromolecule into approximately 1 L of mineral oil, and vigorouslystirring at a temperature no greater than 100° C. for no more than about60 minutes, to achieve dissolution of the star macromolecule, andtesting the solubility at STP.

The term “hydrophilic” is understood to mean, in relation to a material,such as a polymeric arm, or a polymeric segment of a polymeric arm, thatthe material is water soluble and comprises hydrophilic segments havingan HLB equal to or greater than 8, for example, an HLB equal to 16-20,or equal to or greater than 18, 19, or 19.5. In certain embodiments, thehydrophilic segment may comprise at least 75 mol % of water-solublemonomer residues, for example, between 80 mol % to 100 mol % or at least85 mol %, 90 mol %, 95 mol %, or at least 97 mol % water-soluble monomerresidues.

The term “hydrophobic” is understood to mean, in relation to a material,such as a polymeric arm, or a polymeric segment of a polymeric arm, thatthe material is water insoluble and comprises hydrophilic segmentshaving an HLB less than 8, for example, an HLB less than 7. In certainembodiments, the hydrophobic segment may comprise at least 75 mol % ofwater-insoluble monomer residues, for example, between 80 mol % to 100mol % or at least 85 mol %, 90 mol %, 95 mol %, or at least 97 mol %water-insoluble monomer residues.

The term “micelle-philic”, “micelle-philic moiety”, or “micelle-philicpolymeric segment” are understood to mean any moiety, monomer, monomericresidue, or polymeric segment, respectively, having sufficienthydrophobic character to cause the star macromolecule (to which themoiety, monomer, monomeric residue, or polymeric segment is contained)to associate with a micelle in an aqueous environment, for example theassociation may include the moiety incorporating into the micelle, andmay increase the viscosity of the mixture, for example, asurfactant-containing system, such as a surfactant-containing aqueoussystem. Suitable micelle-philic groups may include hydrocarbon groupshaving C₆ or greater tail portion, or fluorine-modified C₄ or greatertail portion. For example, the thickening properties of themicelle-philic, micelle-philic moiety, or micelle-philic polymericsegment, contained within a suitable star macromolecule or polymer maybe determined according to the Thickening and Shear Thinning in WaterTest, the SLES Surfactant Compatibility Test, the Hybrid SLES-CHSurfactant Compatibility Test, the Hybrid CB-SLES SurfactantCompatibility Test, the Hybrid CB-SLES Surfactant with NaClCompatibility Test, the Ritabate 20 Surfactant Compatibility Test, theAPG Surfactant Compatibility Test, the Temperature Stability Test, thepH Efficiency Range in Hybrid CB/SLES Surfactant Test, the pH EfficiencyRange Test, or combinations thereof.

The term “surfactant-system thickening monomer”, “surfactant-systemthickening monomeric residue”, or “surfactant-system thickeningpolymeric segment”, are understood to mean any monomer, monomericresidue, or polymeric segment, respectively, comprising side chainsthat, when contained within a suitable star macromolecule or polymer,may associate, or be modified to associate, with a surfactant in amixture or solution and provide the suitable star macromolecule orpolymer the property to increase the viscosity of thesurfactant-containing system, for example, a surfactant-containingaqueous system, such as an aqueous mixture or an aqueous solution,relative to the absence of the suitable star macromolecule or polymer inthe surfactant-containing system. For example, not wanting to be held toany particular theory, the influence of the surfactant-system thickeningmonomer, surfactant-system thickening monomeric residue, orsurfactant-system thickening polymeric segment, on the suitable starmacromolecules ability to increase the viscosity, or thicken, thesurfactant-containing system may result from said the surfactant-systemthickening monomer, surfactant-system thickening monomeric residue, orsurfactant-system thickening polymeric segment, when contained withinthe suitable star macromolecule or polymer, to associate with or formmicelles when present in the surfactant-containing system. For example,thickening properties of the surfactant-system thickening monomer,surfactant-system thickening monomeric residue, or surfactant-systemthickening polymeric segment, contained within a suitable starmacromolecule or polymer, may be determined according to the Thickeningand Shear Thinning in Water Test, the SLES Surfactant CompatibilityTest, the Hybrid SLES-CH Surfactant Compatibility Test, the HybridCB-SLES Surfactant Compatibility Test, the Hybrid CB-SLES Surfactantwith NaCl Compatibility Test, the Ritabate 20 Surfactant CompatibilityTest, the APG Surfactant Compatibility Test, the Temperature StabilityTest, the pH Efficiency Range in Hybrid CB/SLES Surfactant Test, the pHEfficiency Range Test, or combinations thereof.

The term “surfactant-system thickening star macromolecule” or“surfactant-modified star macromolecule” are understood to mean any starmacromolecule or polymer comprising side chains that may associate, orbe modified to associate, with a surfactant in a mixture or solution andprovide an increase in viscosity of the surfactant-containing system,for example, a surfactant-containing aqueous system, such as an aqueousmixture or an aqueous solution, relative to the absence of the starmacromolecule or polymer in the surfactant-containing system. Forexample, not wanting to be held to any particular theory, increasing theviscosity, or thickening, of the surfactant-containing system may resultfrom the ability of the star macromolecule or polymer to associate withor form micelles when present in the surfactant-containing system. Forexample, thickening properties of a star macromolecule or polymer may bedetermined according to the Thickening and Shear Thinning in Water Test,the SLES Surfactant Compatibility Test, the Hybrid SLES-CH SurfactantCompatibility Test, the Hybrid CB-SLES Surfactant Compatibility Test,the Hybrid CB-SLES Surfactant with NaCl Compatibility Test, the Ritabate20 Surfactant Compatibility Test, the APG Surfactant Compatibility Test,the Temperature Stability Test, the pH Efficiency Range in HybridCB/SLES Surfactant Test, the pH Efficiency Range Test, or combinationsthereof.

The term “monomer residue” or “monomeric residue” is understood to meanthe residue resulting from the polymerization of the correspondingmonomer. For example, a polymer derived from the polymerization of anacrylic acid monomer (or derivatives thereof, such as acid protectedderivatives of acrylic acid including but not limited to t-butyl esterof acrylic acid), will provide polymeric segments, identified as PAA,comprising repeat units of monomeric residues of acrylic acid, i.e.,“—CH(CO₂H)CH₂—”. For example, a polymer derived from the polymerizationof styrene monomers will provide polymeric segments, identified as PSt,comprising repeat units of monomeric residues of styrene, i.e.,“—CH(C₆H₅)CH₂—.” For example, a polymer derived from the polymerizationof monomeric divinylbenzene monomers will provide polymeric segmentscomprising repeat units of monomeric residues of divinylbenzene, i.e.,“—CH₂CH(C₆H₅)CHCH₂—.”

The term “emulsifier” is understood to mean a component that comprisesan appreciable weight percent of an amphiphilic compound having amolecular weight of less than 5,000 MW. Emulsifiers are usually linearorganic compounds that contain both hydrophobic portions (tails) andhydrophilic portions (heads), i.e., are amphiphilic. Examples ofemulsifiers include but are not limited to: alkyl benzenesulfonates,alkanesulfonates, olefin sulfonates, alkylethersulfonates, glycerolether sulfonates, α-methyl ester sulfonates, sulfofatty acids, alkylsulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide(ether) sulfates, mono- and dialkylsulfosuccinates, mono- anddialkylsulfosuccinamates, sulfotriglycerides, ether carboxylic acids andsalts thereof, fatty acid isethionates, fatty acid sarcosinates, fattyacid taurides, acyl lactylates, acyl tartrates, acyl glutamates, acylaspartates, alkyl oligoglucoside sulfates, protein fatty acidcondensates (particularly wheat-based vegetable products) and alkyl(ether) phosphates, alkylbetaines, alkylamidobetaines, aminopropionates,aminoglycinates, imidazoliniumbetaines and sulfobetaines.

The term “emulsifier-free” is understood to mean a composition ormixture wherein the formulation is substantially devoid of anyemulsifiers, for example less than 0.1 wt. % of emulsifier, relative tothe total composition, or less than 0.05 wt. % of emulsifier, relativeto the total composition, or less than 0.01 wt. % of emulsifier,relative to the total composition, or a formulation where there is noemulsifier.

The term “degradable unit” is understood to mean one or more chemicalbonds within the star macromolecule that breaks when exposed to abreaker or a breaker environment. For example, a degradable unit mayinclude an ester bond, an amide bond, a peptide bond, an ether bond, adisuphide bond, a phosphate ester bond, or a siloxane bond. In certainembodiments, one or more degradable units may be present in the core, inthe polymeric arms, in the polymeric segments, at the junctions joiningthe polymeric arms to the core, in the side chains of the monomericresidues of the polymeric arms or polymeric segments, or combinationsthereof.

The term “breaker” is understood to mean an agent or additive, such as achemical, that breaks one or more chemical bonds within a degradableunit or units. For example, a breaker may include: acids, such asmineral acids, for example hydrochloric acid, acetic acid, phosphoricacid, sulfuric acid, or hydrofluoric acid; bases, such as alkali metalhydroxides, for example sodium hydroxide or potassium hydroxide,alkaline earth metal hydroxides, or ammonium hydroxide; enzymes, such asany enzyme capable of breaking a chemical bond comprised of a degradableunit; oxidizing agents, such as ammonium peroxide, hydrogen peroxide,degradation products of glucose or other sugars, or bleach; salts, suchas salts containing alkali metal ions, such as sodium or potassium ions,for example sodium carbonate; alkaline earth metal ions, such as calciumor magnesium ions; ammonium ions; carbonate ions; hydrogen carbonateions; phosphate ions; silicate ions; halogen ions, such as chloride orfluoride ions, for example sodium chloride, potassium chloride, ormagnesium chloride; or minerals.

The term “breaker environment” is understood to mean a stimulienvironment that causes a decrease in the viscosity of a mixture orsolution either by making the conditions or local environment of themixture or solution such that the star macromolecule or polymer has areduced ability or is no longer able to thicken, and/or breaks orfacilitates the breaking of chemical bonds, comprised of degradableunits, contained within a star macromolecule or polymer, resulting in adecrease in viscosity of the mixture or solution.

The term “stimuli environment” is understood to include temperature(e.g., at high temperatures, for example, temperatures greater than 450°F., such as greater than 600° F., or greater than 800° F.; or at lowtemperatures, for example, less than −30° F., such as less than −50° F.,or less than −50° F.), salinity (e.g., at high salt concentrations, forexample, at greater than 3 wt. %, such as greater than 5 wt. %, greaterthan 10 wt. %, greater than 15 wt. %, greater than 20 wt. %, or greaterthan 25 wt. %), mechanical (e.g., at high shear rates), photo (eitherlight or dark), or chemical (e.g., at high or low pH, or other chemicaltrigger).

In certain embodiments, the polymer composition, the number of polymericarms on any particular star macromolecule varies across the populationof star macromolecules in each composition, due to the synthetic processused for the synthesis of the composition. This process is called “armfirst” method and is described in details herein below. Due to variationin the number of polymeric arms in star macromolecules, the number ofpolymeric arms, such as the number of polymeric arms r, s and/or t, arereferred as an average number of polymeric arms. Monomer units withinthe polymeric arms or core of the star macromolecule of the presentinvention may be connected with C—C covalent bonds. In certainembodiments, the C—C covalent bonds may make it difficult to degradesuch that the star macromolecule may perform as efficient thickeningagent in a harsh environment, for example, a very high/low pH or in thepresence of strong oxidizing agents.

In certain embodiments, a surfactant-system thickening macromolecule isprovided that is suitable for increasing the viscosity of asurfactant-containing system, wherein the surfactant-system thickeningmacromolecule comprises:

-   -   a) a core;    -   b) at least one first polymeric arm, comprising a hydrophilic        polymeric segment covalently attached to the core; and    -   c) at least one second polymeric arm, comprising:        -   i) a hydrophilic polymeric segment covalently attached to            the core; and        -   ii) a further segment covalently attached to the hydrophilic            polymeric segment, wherein the further segment is comprised            of at least one monomeric residue of a polymerized            surfactant-system thickening monomer comprising a C₆ or            greater alkyl acrylate; C₆ or greater alkenyl acrylate; C₆            or greater alkyl alkyl acrylate; C₆ or greater alkenyl alkyl            acrylate; C₆ or greater alkyl acrylamide; C₆ or greater            alkenyl acrylamide; C₆ or greater alkyl alkyl acrylamide; C₆            or greater alkenyl alkyl acrylamide; C₂ or greater alkyl            vinyl ether, C₂ or greater alkenyl vinyl ether, C₁ or            greater alkyl allyl ether, or C₁ or greater alkenyl allyl            ether.

In certain embodiments, the surfactant-system thickening macromoleculemay be represented by Formula A:

[(P1)_(q)]_(r)-Core-[(P3)_(q3)-(P2)_(q2)],  Formula A

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents a polymeric segment of a first        polymeric arm comprised of monomeric residues of polymerized        hydrophilic monomers;    -   P2 independently represents a further segment of a second        polymeric arm comprised of at least one monomeric residue of a        polymerized surfactant-system thickening monomer;    -   P3 independently represents a polymeric segment of the second        polymeric arm comprised of monomeric residues of polymerized        hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   r independently represents the number of the first polymeric        arms covalently attached to the Core; and    -   s independently represents the number of the second polymeric        arms covalently attached to the Core.

In certain embodiments, the surfactant-system thickening macromoleculemay be represented by Formula B:

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents a polymeric segment of a first        polymeric arm comprised of monomeric residues of polymerized        hydrophilic monomers;    -   P2 independently represents a further segment of a second        polymeric arm comprised of at least one monomeric residue of a        polymerized surfactant-system thickening monomer;    -   P3 independently represents a polymeric segment of the second        polymeric arm comprised of monomeric residues of polymerized        hydrophilic monomers;    -   P4 independently represents a polymeric segment of a third        polymeric arm comprised of monomeric residues of polymerized        hydrophobic monomers;    -   P5 independently represents a polymeric segment of the third        polymeric arm comprised of monomeric residues of polymerized        hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   q4 independently represents the number of monomeric residues in        P4;    -   q5 independently represents the number of monomeric residues in        P5;    -   r independently represents the number of the first polymeric        arms covalently attached to the Core;    -   s independently represents the number of the second polymeric        arms covalently attached to the Core; and    -   t independently represents the number of the third polymeric        arms covalently attached to the Core.

In certain embodiments, a surfactant-modified star macromolecule isprovided that may comprise:

-   -   i) a core;    -   ii) at least one first polymeric arm, comprising a hydrophilic        polymeric segment covalently attached to the core; and    -   iii) at least one second polymeric arm, comprising:        -   a) a hydrophilic polymeric segment covalently attached to            the core; and        -   b) a further segment comprising at least one pendant moiety            represented by [L¹-G¹-L²-G²];            wherein:    -   G¹ independently represents a residue of a hydrophilic moiety of        the surfactant;    -   G² independently represents a residue of a hydrophobic moiety of        the surfactant;    -   L¹ independently represents a linking group or a covalent bond,        attaching G¹ to the further segment; and    -   L² independently represents a linking group or a covalent bond,        linking G¹ and G².

In certain embodiments, a method of increasing the viscosity of asurfactant-containing aqueous system may comprise introducing asurfactant-system thickening macromolecule into thesurfactant-containing aqueous system, wherein the surfactant-systemthickening macromolecule may be represented by Formula C:

[(P1)_(q1)]_(r)-Core-[(P3)_(q3)-(P2)_(q2)],  Formula C

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents a polymeric segment of the at least        one first polymeric arm comprised of monomeric residues of        polymerized hydrophilic monomers;    -   P2 independently represents a further segment of the at least        one second polymeric arm comprised of:        -   1) a polymerized backbone comprising at least one pendant            micelle-philic moiety, or        -   2) at least one monomeric residue of a polymerized            micelle-philic monomer,    -   P3 independently represents a polymeric segment of the at least        one second polymeric arm comprised of monomeric residues of        polymerized hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   r independently represents the number of the at least one first        polymeric arms covalently attached to the Core; and    -   s independently represents the number of the at least one second        polymeric arms covalently attached to the Core.

In certain embodiments, a method of increasing the viscosity of asurfactant-containing aqueous system may comprise introducing asurfactant-system thickening macromolecule into thesurfactant-containing aqueous system, wherein the surfactant-systemthickening macromolecule may be represented by Formula D:

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents a polymeric segment of the at least        one first polymeric arm comprised of monomeric residues of        polymerized hydrophilic monomers;    -   P2 independently represents a further segment of the at least        one second polymeric arm comprised of:        -   1) a polymerized backbone comprising at least one pendant            micelle-philic moiety, or        -   2) at least one monomeric residue of a polymerized            micelle-philic monomer,    -   P3 independently represents a polymeric segment of the at least        one second polymeric arm comprised of monomeric residues of        polymerized hydrophilic monomers;    -   P4 independently represents a polymeric segment of the at least        one third polymeric arm comprised of monomeric residues of        polymerized hydrophobic monomers;    -   P5 independently represents a polymeric segment of the at least        one third polymeric arm comprised of monomeric residues of        polymerized hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   q4 independently represents the number of monomeric residues in        P4;    -   q5 independently represents the number of monomeric residues in        P5;    -   r independently represents the number of the at least one first        polymeric arms covalently attached to the Core;    -   s independently represents the number of the at least one second        polymeric arms covalently attached to the Core; and    -   t independently represents the number of the at least one third        polymeric arms covalently attached to the Core.

In certain embodiments, a method of increasing the viscosity of asurfactant-containing aqueous system may comprise introducing asurfactant-system thickening macromolecule into thesurfactant-containing aqueous system, wherein the surfactant-systemthickening macromolecule may comprise:

-   -   a) a core;    -   b) at least one first polymeric arm, comprising a hydrophilic        polymeric segment covalently attached to the core; and    -   c) at least one second polymeric arm, comprising:        -   i) a hydrophilic polymeric segment covalently attached to            the core; and        -   ii) a further segment covalently attached to the hydrophilic            polymeric segment, wherein the further segment is comprised            of at least one monomeric residue of a polymerized            surfactant-system thickening monomer comprising a C₆ or            greater alkyl acrylate; C₆ or greater alkenyl acrylate; C₆            or greater alkyl alkyl acrylate; C₆ or greater alkenyl alkyl            acrylate; C₆ or greater alkyl acrylamide; C₆ or greater            alkenyl acrylamide; C₆ or greater alkyl alkyl acrylamide; C₆            or greater alkenyl alkyl acrylamide; C₂ or greater alkyl            vinyl ether, C₂ or greater alkenyl vinyl ether, C₁ or            greater alkyl allyl ether, or C₁ or greater alkenyl allyl            ether.

In certain embodiments, a method of increasing the viscosity of asurfactant-containing aqueous system may comprise introducing asurfactant-modified star macromolecule into the surfactant-containingaqueous system, wherein the surfactant-modified star macromolecule maycomprise:

-   -   i) a core;    -   ii) at least one first polymeric arm, comprising a hydrophilic        polymeric segment covalently attached to the core; and    -   iii) at least one second polymeric arm, comprising:        -   a) a hydrophilic polymeric segment covalently attached to            the core; and        -   b) a further segment comprising at least one pendant moiety            represented by [L¹-G¹-L²-G²];            wherein:    -   G¹ independently represents a residue of a hydrophilic moiety of        the surfactant;    -   G² independently represents a residue of a hydrophobic moiety of        the surfactant;    -   L¹ independently represents a linking group or a covalent bond,        attaching G¹ to the further segment; and    -   L² independently represents a linking group or a covalent bond,        linking G¹ and G².

In certain embodiments, the core of the star macromolecule may be acrosslinked core, such as a crosslinked polymeric core or a hydrophobiccrosslinked polymeric core. Suitable crosslinking monomers for the coreencompass all of the compounds which are capable, under thepolymerization conditions, of bringing about crosslinking. Suitablecrosslinking monomers include, but are not limited to, di- andmulti-functional crosslinkers, such as di-, tri-, tetra-, penta-, orhexa-functional crosslinkiers, for example, di-, tri-, tetra-functional(meth)acrylates, di-, tri- and tetra-functional styrenes and othermulti- or poly-functional crosslinkers. Suitable crosslinking monomersthat may be used to form a core of a star macromolecule may include, butare not limited to, a multifunctional monomer, for example, ahexafunctional monomer, a pentafunctional monomer, a tetrafunctionalmonomer, a trifunctional monomer, or a difunctional monomer. Forexample, a crosslinking monomer may be a hydrophobic monomer or ahydrophilic monomer, such as a hydrophobic multifunctional monomer or ahydrophilic multifunctional monomer, for example, a hydrophobicdifunctional monomer or a hydrophilic difunctional monomer. For example,the crosslinking monomers may be a hydrophobic crosslinker, including,but not limited to, 1,2-divinylbenzene; 1,3-divinylbenzene;1,4-divinylbenzene; 1,2-ethanediol di(meth)acrylate; 1,3-propanedioldi(meth)acrylate; 1,4-butanediol di(meth)acrylate; 1,5-hexanedioldi(meth)acrylate; divinylbenzene; ethyleneglycol di(meth)acrylate;di(ethylene glycol) diacrylate (DEGlyDA); propyleneglycoldi(meth)acrylate; butyleneglycol di(meth)acrylate; triethyleneglycoldi(meth)acrylate; polyethyleneglycol di(meth)acrylate;polypropyleneglycol di(meth)acrylate; polybutyleneglycoldi(meth)acrylate; allyl(meth)acrylate; glycerol di(meth)acrylate;trimethylolpropane tri(meth)acrylate; pentaerythritoltetra(meth)acrylate; allyl methacrylate; or allyl acrylate. For example,the crosslinking monomer may be di(ethylene glycol) diacrylate (DEGlyDA)or divinylbenzene. For example, the crosslinking monomer may bedivinylbenzene.

In certain embodiments, the star macromolecule may comprise multiplepolymeric arms, for example, star macromolecule may comprise an averagenumber of polymeric arms in the range of between 5 and 5,000 polymericarms, such as between 10 and 250; between 10 and 500; between 10 and750; between 500 and 750; between 10 and 1,000; between 10 and 2,500;between 200 and 5,000; between 200 and 4,000; between 200 and 2,000;between 200 and 1,000; between 200 and 750; between 500 and 5,000;between 600 and 1,500; between 600 and 2,000; between 600 and 3,000;between 2,500 and 5,000; between 1,000 and 2,500; between 1,500 and3,000; between 550 and 1,000; between 550 and 2,000; between 550 and3,000; between 550 and 4,000; between 550 and 5,000.

In certain embodiments, the polymeric arms of the star macromolecule maycomprise a hydrophilic polymeric segment, such as a water solublepolymeric segment, a hydrophobic polymeric segment, or asurfactant-system thickening polymeric segment. The hydrophilicpolymeric segment, for example, may be a water soluble polymericsegment, and may comprise a poly(acrylic acid), poly(2-hydroxyethylacrylate), poly(N-isopropylacrylamide), poly(ethylene glycol)methacrylate, or quaternized poly(dimethylaminoethyl methacrylate),polymeric segments. The hydrophobic polymeric segment, for example, maycomprise polystyrene or substituted polystyrenes,poly(alkyl(meth)acrylate) or a hydrocarbon-based polymeric segments.Suitable hydrocarbon-based segments may comprise low molecular weightα-olefin. Lower molecular weight α-olefins are commercially availableand higher molecular weight species may be prepared by telomerization ofethylene or ethylene propylene mixtures. [Kaneyoshi, H.; Inoue, Y.;Matyjaszewski, K. Macromolecules 2005, 38, 5425-5435.]

Suitable hydrophilic monomers that may be used to form a polymeric armor a segment of a polymeric arm, for example, a polymeric segment of apolymeric arm, such as for P1, P3, or P5 (or optionally within P2), of astar macromolecule may include, but is not limited to,2-acrylamido-2-methylpropane sulfonic acid (AMPS), styrene sulphonicacid, protected and unprotected acrylic acids and methacrylic acidsincluding: acrylic acid, methacrylic acid, ethacrylic acid, methylacrylate, ethyl acrylate, α-butyl acrylate, iso-butyl acrylate, t-butylacrylate, 2-ethylhexyl acrylate, decyl acrylate, octyl acrylate; methylmethacrylate; ethyl methacrylate; n-butyl methacrylate; iso-butylmethacrylate; t-butyl methacrylate; 2-ethylhexyl methacrylate; decylmethacrylate; methyl ethacrylate; ethyl ethacrylate; n-butylethacrylate; iso-butyl ethacrylate; t-butyl ethacrylate; 2-ethylhexylethacrylate; decyl ethacrylate; 2,3-dihydroxypropyl acrylate;2,3-dihydroxypropyl methacrylate; 2-hydroxyethyl acrylate;2-hydroxypropyl acrylate; hydroxypropyl methacrylate; glycerylmonoacrylate; glyceryl monoethacrylate; glycidyl methacrylate; glycidylacrylate; acrylamide; methacrylamide; ethacrylamide; N-methylacrylamide; N,N-dimethyl acrylamide; N,N-dimethyl methacrylamide;N-ethyl acrylamide; N-isopropyl acrylamide; N-butyl acrylamide;N-t-butyl acrylamide; N,N-di-n-butyl acrylamide; N,N-diethylacrylamide;N-octyl acrylamide; N-octadecyl acrylamide; N,N-diethylacrylamide;N-phenyl acrylamide; N-methyl methacrylamide; N-ethyl methacrylamide;N-dodecyl methacrylamide; N,N-dimethylaminoethyl acrylamide; quaternisedN,N-dimethylaminoethyl acrylamide; N,N-dimethylaminoethylmethacrylamide; quaternised N,N-dimethylaminoethyl methacrylamide;N,N-dimethylaminoethyl acrylate; N,N-dimethylaminoethyl methacrylate;quaternised N,N-dimethyl-aminoethyl acrylate; quaternisedN,N-dimethylaminoethyl methacrylate; 2-hydroxyethyl acrylate;2-hydroxyethyl methacrylate; 2-hydroxyethyl ethacrylate; glycerylacrylate; 2-methoxyethyl acrylate; 2-methoxyethyl methacrylate;2-methoxyethyl ethacrylate; 2-ethoxyethyl acrylate; 2-ethoxyethylmethacrylate; 2-ethoxyethyl ethacrylate; maleic acid; maleic anhydrideand its half esters; fumaric acid; itaconic acid; itaconic anhydride andits half esters; crotonic acid; angelic acid; diallyldimethyl ammoniumchloride; vinyl pyrrolidone vinyl imidazole; methyl vinyl ether; methylvinyl ketone; maleimide; vinyl pyridine; vinyl pyridine-N-oxide; vinylfuran; styrene sulphonic acid and its salts; allyl alcohol; allylcitrate; allyl tartrate; vinyl acetate; vinyl alcohol; vinylcaprolactam; vinyl acetamide; or vinyl formamide. For example, thehydrophilic monomer may comprise protected and unprotected acrylic acid,such as methacrylic acid, ethacrylic acid, methyl acrylate, ethylacrylate, α-butyl acrylate, iso-butyl acrylate, t-butyl acrylate,2-ethylhexyl acrylate, decyl acrylate, octyl acrylate; methyl acrylate;methyl methacrylate; methyl ethacrylate; ethyl acrylate; ethylmethacrylate; ethyl ethacrylate; n-butyl acrylate; n-butyl methacrylate;n-butyl ethacrylate; 2-ethylhexyl acrylate; 2-ethylhexyl methacrylate;2-ethylhexyl ethacrylate; N-octyl acrylamide; 2-methoxyethyl acrylate;2-hydroxyethyl acrylate; N,N-dimethylaminoethyl acrylate;N,N-dimethylaminoethyl methacrylate; acrylic acid; methacrylic acid;N-t-butylacrylamide; N-sec-butylacrylamide; N,N-dimethylacrylamide;N,N-dibutylacrylamide; N,N-dihydroxyethyllacrylamide; 2-hydroxyethylacrylate; 2-hydroxyethyl methacrylate; benzyl acrylate;4-butoxycarbonylphenyl acrylate; butyl acrylate; 4-cyanobutyl acrylate;cyclohexyl acrylate; dodecyl acrylate; 2-ethylhexyl acrylate; heptylacrylate; iso-butyl acrylate; 3-methoxybutyl acrylate; 3-methoxypropylacrylate; methyl acrylate; N-butyl acrylamide; N,N-dibutyl acrylamide;ethyl acrylate; methoxyethyl acrylate; hydroxyethyl acrylate; ordiethyleneglycolethyl acrylate. For example, the hydrophilic monomer maycomprise protected and unprotected acrylic acid, such as methacrylicacid, ethacrylic acid, methyl acrylate, ethyl acrylate, α-butylacrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate,decyl acrylate, octyl acrylate; 2-hydroxyethyl acrylate;N-isopropylacrylamide; ethylene glycol methacrylate; (polyethyleneglycol) methacrylate; or quaternized dimethylaminoethyl methacrylate.For example, the hydrophilic monomer may comprise acrylic acid,methacrylic acid, 2-hydroxyethyl acrylate, acrylamide, vinylpyrrolidone, vinyl pyridine, styrene sulphonic acid, PEG-methacrylate,2-(dimethylamino)ethyl methacrylate, 2-(trimethylamino)ethylmethacrylate, 2-acrylamido-2-methylpropane sulphonic acid, acrylic acid,acrylic anhydride, beta-carboxyethyl acrylate, methacrylic acid,4-methacryloxyethyl trimellitic anhydride, 3-methacryloyl-(1)-lysine,o-nitrobenzyl methacrylate, 2-propene-1-sulfonic acid, 2-sulfoethylmethacrylate, trichloroacrylic acid, 4-vinylbenzoic acid, acrylamides,2-(N,N-dimethylamino)-ethyl acrylate,N-[2-N,N-dimethylamino)-ethyl]methacrylamide,2-(N,N-dimethylamino)-ethyl methacrylate,3-dimethylaminoneopentylacrylate, N-[3-(N,N-methylamino)-propyl]acrylamide, N-[3-(N,N-Dimethylamino)-propyl] methacrylamide,2-N-morpholinoethyl acrylate, 2-N-morpholinoethyl methacrylate,3-methacryloyl-(1)-lysine, N,N-diallylamine, diallyldimethyl,2-aminoethyl methacrylamide, N-(2-aminoethyl) methacrylamidehydrochloride, N-(3-aminopropyl)-methacrylamide hydrochloride,N-(t-BOC-aminopropyl)-acrylamide, 2-(t-butylamino)ethyl methacrylate,2-(N,N-diethylamino)-ethyl methacrylate (DEAEMA),2-diisopropylaminoethyl methacrylate. For example, the hydrophilicmonomer may comprise acrylic acid.

Suitable hydrophobic monomers that may be used to form a polymeric armor a segment of a polymeric arm, for example, a polymeric segment of apolymeric arm, such as for P4 (or optionally within P2), of a starmacromolecule may include, but is not limited to styrene, methylacrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butylacrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, methylmethacrylate; ethyl methacrylate; n-butyl methacrylate; iso-butylmethacrylate; t-butyl methacrylate; 2-ethylhexyl methacrylate; octylmethacrylate, decyl methacrylate, methyl ethacrylate; ethyl ethacrylate;n-butyl ethacrylate; iso-butyl ethacrylate; t-butyl ethacrylate;2-ethylhexyl ethacrylate; octyl ethacrylate, decyl ethacrylate,2,3-dihydroxypropyl acrylate; 2,3-dihydroxypropyl methacrylate;2-hydroxypropyl acrylate; hydroxypropyl methacrylate; glycidylmethacrylate; glycidyl acrylate, acrylamides, styrene; styreneoptionally substituted with one or more C₁-C₁₂ straight or branchedchain alkyl groups; or alkylacrylate. For example, the hydrophobicmonomer may comprise styrene; alpha-methylstyrene; t-butylstyrene;p-methylstyrene; methyl methacrylate; or t-butyl-acrylate. For example,the hydrophobic monomer may comprise styrene. In certain embodiments,the hydrophobic monomer may comprise a protected functional group.

In certain embodiments, suitable surfactant-system thickening monomersthat may be used to form a surfactant-system thickening polymericsegment, for example, to form polymeric segment P2, may include, but arenot limited to, alkyl acrylates, acrylamides, styrenes, vinyl pyridines,vinyl ethers, and allyl ethers. For example, the suitablesurfactant-system thickening monomers may be represented by one of thefollowing Formulas (I)-(V):

wherein:

-   -   R¹, R², and R³ independently represent hydrogen, methyl, ethyl,        or C₃₋₁₈ alkyl, for example C₃₋₆ alkyl, C₆₋₁₂ alkyl, or C₁₂₋₁₈        alkyl; wherein the alkyl may be branched or unbranched, linear        or cyclic, and may be optionally substituted with one or more        halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol);    -   R⁴ and R⁷ independently represent C₁₃ or greater alkyl, —C₆ or        greater alkyl-(O—C₁₋₆ alkyl)_(n), C₆ or greater alkenyl, or C₆        or greater alkenyl-(O—C₁₋₆ alkyl)_(n); or when R³ is C₁ or        greater, then R⁴ may independently represent C₁₁ or greater        alkyl, —C₆ or greater alkyl —(O—C₁₋₆ alkyl)_(n), C₆ or greater        alkenyl, or C₆ or greater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein        each alkyl portion independently may be branched or unbranched,        linear or cyclic, saturated or unsaturated, and may be        optionally substituted with one or more halogens, C₁₋₆ alkoxy        groups, or poly(ethylene glycol);    -   R⁵ independently represents C₁₉ or greater alkyl, —C₆ or greater        alkyl —(O—C₁₋₆ alkyl)_(n), C₆ or greater alkenyl, or C₆ or        greater alkenyl-(O—C₁₋₆ alkyl)_(n); or when R⁶ is C₁ or greater,        then R⁵ may independently represent C₁₃ or greater alkyl, —C₆ or        greater alkyl —(O—C₁₋₆ alkyl)_(n), C₆ or greater alkenyl, or C₆        or greater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkyl        portion independently may be branched or unbranched, linear or        cyclic, saturated or unsaturated, and may be optionally        substituted with one or more halogens, C₁₋₆ alkoxy groups, or        poly(ethylene glycol);    -   R⁶ independently represents hydrogen, C₁₋₁₈ alkyl, —C₁₋₁₈        alkyl-(O—C₁₋₆ alkyl)_(n), or is R⁴, or is R⁵; wherein each alkyl        portion independently may be branched or unbranched, linear or        cyclic, saturated or unsaturated, and may be optionally        substituted with one or more halogens, C₁₋₆ alkoxy groups, or        poly(ethylene glycol);    -   R⁸ independently represents C₂ or greater alkyl, —C₂ or greater        alkyl-(O—C₁₋₆ alkyl)_(n), C₃ or greater alkenyl, —C₃ or greater        alkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkyl portion        independently may be branched or unbranched, linear or cyclic,        saturated or unsaturated, and may be optionally substituted with        one or more halogens, C₁₋₆ alkoxy groups, or poly(ethylene        glycol);    -   R⁹ independently represents C₁ or greater alkyl, —C₁ or greater        alkyl-(O—C₁₋₆ alkyl)_(n), C₃ or greater alkenyl, —C₃ or greater        alkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkyl portion        independently may be branched or unbranched, linear or cyclic,        saturated or unsaturated, and may be optionally substituted with        one or more halogens, C₁₋₆ alkoxy groups, or poly(ethylene        glycol); or    -   R⁴, R⁵, R⁷, R⁸, R⁹ independently represent a hydrophobic portion        of a surfactant, a hydrophobic portion of a lipid, or a        hydrophobic portion of a fatty alcohol;    -   A¹, A², A³ and A⁴ independently represent CH, CR¹⁰, or N,        wherein at least two of A¹, A², A³ and A⁴ is CH or CR¹⁰;    -   R¹⁰ independently represents hydrogen, C₁₋₁₀ alkyl, halogen,        hydroxyl, C₁₋₁₀ alkoxy; wherein the alkyl or alkoxy may be        branched or unbranched, linear or cyclic, and may be optionally        substituted with one or more halogens, C₁₋₆ alkoxy groups, or        poly(ethylene glycol);    -   Y independently represents a covalent bond, —O—, —S—, —N(H)—,        —N(R¹)—, —(CO)—, —S(O)—, —S(O)₂—, —S(O)₂N(R¹)—, —(CO)N(R¹)—,        —N(R¹)—(CO)—, —(CO)O—, or —O—(CO)—;    -   L¹ independently represents a covalent bond, ethylene glycol,        poly(ethylene glycol), polyether, polyamide, C₁₋₆ alkyl,        —(CO)N(R¹)—, —N(R¹)—(CO)—, —(CO)O—, —O—(CO)—, or combinations        thereof, or is independently absent; or    -   L¹ independently represents a hydrophilic portion of a        surfactant, a hydrophilic portion of a lipid, or a hydrophilic        portion of a fatty alcohol;    -   L² independently represents (CH₂)₁₋₄₀, C₁₋₄₀ alkyl, (O—C₂₋₆        alkyl)_(n), or (C₂₋₆ alkyl)-(O—C₂₋₆ alkyl)_(n); wherein the        alkyl may be branched or unbranched, linear or cyclic, and may        be optionally substituted with one or more halogens, C₁₋₆ alkoxy        groups, or poly(ethylene glycol); and    -   n independently represents a value in the range of 1-1000.

In certain embodiments, R¹, R², and R³ may independently representhydrogen, methyl, ethyl, or C₃₋₁₈ alkyl, for example C₃₋₆ alkyl, C₆₋₁₂alkyl, or C₁₂₋₁₈ alkyl; wherein the alkyl may be branched or unbranched,linear or cyclic. In certain embodiments, R¹ and R² may independentlyrepresent hydrogen or methyl. In certain embodiments, R¹ and R² mayindependently represent C₃₋₆ alkyl, C₆₋₁₂ alkyl, or C₁₂₋₁₈ alkyl;wherein the alkyl may be branched or unbranched, linear or cyclic, andmay be optionally substituted with one or more halogens, C₁₋₆ alkoxygroups, or poly(ethylene glycol).

In certain embodiments, R⁴ of the acrylate represented by Formula (I)may include, but is not limited to, a C₁₃ or greater alkyl acrylate;C₁₃₋₄₀ alkyl acrylate; C₁₄ or greater alkyl acrylate; C₁₆ or greateralkyl acrylate; C₁₈ or greater alkyl acrylate; C₁₁ or greater alkylalkyl acrylate; C₁₁-4a alkyl alkyl acrylate; C₁₄ or greater alkyl alkylacrylate; C₁₆ or greater alkyl alkyl acrylate; or C₁₈ or greater alkylalkyl acrylate. For example, the alkyl acrylate represented by Formula(I) may include, but is not limited to, 10-undecenyl acrylate, laurylacrylate, tridecyl acrylate, hexadecyl acrylate, stearyl acrylate, orbehenyl acrylate. For example, an alkyl methacrylate represented byFormula (I) may include, but is not limited to, lauryl methacrylate,tridecyl methacrylate, hexadecyl methacylate, stearyl methacrylate,behenyl methacrylate, or poly(ethylene glycol) behenyl ethermethacrylate. For example, an alkyl ethacrylate represented by Formula(I) may include, but is not limited to, lauryl ethacrylate, tridecylethacrylate, hexadecyl ethacrylate, or stearyl ethacrylate. In certainembodiments, R⁴ of an acrylate represented by Formula (I) may include,but is not limited to, a saturated fatty alkyl moiety comprising:tridecyl, isotridecyl, myristyl, pentadecyl, cetyl, palmityl,heptadecyl, stearyl, nonadecyl, arachidyl, heneicosyl, behenyl,lignoceryl, ceryl (heptacosanyl), montanyl, nonacosanyl, myricyl,dotriacontanyl, geddyl, or cetostearyl moiety.

In certain embodiments, R⁴ of the acrylate represented by Formula (I)may include, but is not limited to, a —C₆ or greater alkyl-(O—C₁₋₆alkyl)_(n), or C₆ or greater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein the —C₆or greater alkyl may be C₆₋₁₂ alkyl, C₁₁₋₂₀ alkyl, C₁₈₋₃₀ alkyl, orC₂₀₋₄₀ alkyl; wherein the —C₆ or greater alkenyl may be C₆₋₁₂ alkenyl,C₁₁₋₂₀ alkenyl, C₁₈₋₃₀ alkenyl, or C₂₀₋₄₀ alkenyl; wherein each alkylportion independently may be branched or unbranched, linear or cyclic,saturated or unsaturated, and may be optionally substituted with one ormore halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol); whereineach alkenyl portion independently may be branched or unbranched, linearor cyclic, mono- or poly-unsaturated, conjugated or unconjugated, andmay be optionally substituted with one or more halogens, C₁₋₆ alkoxygroups, or poly(ethylene glycol).

In certain embodiments, R⁴ of the acrylate represented by Formula (I)may include, but is not limited to, a C₆ or greater alkenyl acrylate;C₆₋₄₀ alkenyl acrylate; C₈ or greater alkenyl acrylate; C₁₀ or greateralkenyl acrylate; C₁₂ or greater alkenyl acrylate; C₁₄ or greateralkenyl acrylate; C₁₈ or greater alkenyl acrylate; C₆ or greater alkenylalkyl acrylate; C₆₋₄₀ alkenyl alkyl acrylate; C₈ or greater alkenylalkyl acrylate; C₁₀ or greater alkenyl alkyl acrylate; C₁₂ or greateralkenyl alkyl acrylate; C₁₄ or greater alkenyl alkyl acrylate; or C₁₈ orgreater alkenyl alkyl acrylate. For example, R⁴ of an acrylaterepresented by Formula (I) may include, but is not limited to, anunsaturated fatty alkyl moiety comprising either a mono- or polyunsaturated fatty alkyl moiety, such as di-, tri, tetra, penta, orhexa-unsaturated fatty alkyl moiety. In certain embodiments, theunsaturated fatty alkyl moiety may comprise: myristoleyl, palmitoleyl,sapienyl, oleyl, elaidyl, vaccenyl, linoleyl, linoelaidyl, α-linolenyl,arachidonyl, eicosapentaenoyl, erucyl, or docosahexaenoyl moiety.

In certain embodiments, R⁵ of the acrylamide represented by Formula (II)may include, but is not limited to, a C₁₉ or greater alkyl acrylamide;C₁₉₋₄₀ alkyl acrylamide; C₁₉ or greater alkyl acrylamide; C₁₉ or greateralkyl acrylamide; C₁₉ or greater alkyl acrylamide; C₁₃ or greater alkylalkyl acrylamide; C₁₃₋₄₀ alkyl alkyl acrylamide; C₁₄ or greater alkylalkyl acrylamide; C₁₆ or greater alkyl alkyl acrylamide; or C₁₈ orgreater alkyl alkyl acrylamide. In certain embodiments, R⁵ of anacrylamide represented by Formula (II) may include, but is not limitedto, a saturated fatty alkyl moiety, such as a tridecyl, isotridecyl,myristyl, pentadecyl, cetyl, palmityl, heptadecyl, stearyl, nonadecyl,arachidyl, heneicosyl, behenyl, lignoceryl, ceryl (heptacosanyl),montanyl, nonacosanyl, myricyl, dotriacontanyl, geddyl, or cetostearylmoiety.

In certain embodiments, R⁵ of an acrylamide represented by Formula (II)may include, but is not limited to, a C₆ or greater alkenyl acrylamide;C₆₋₄₀ alkenyl acrylamide; C₈ or greater alkenyl acrylamide; C₁₀ orgreater alkenyl acrylamide; C₁₂ or greater alkenyl acrylamide; C₁₄ orgreater alkenyl acrylamide; C₁₈ or greater alkenyl acrylamide; C₆ orgreater alkenyl alkyl acrylamide; C₆₋₄₀ alkenyl alkyl acrylamide; C₈ orgreater alkenyl alkyl acrylamide; C₁₀ or greater alkenyl alkylacrylamide; C₁₂ or greater alkenyl alkyl acrylamide; C₁₄ or greateralkenyl alkyl acrylamide; or C₁₈ or greater alkenyl alkyl acrylamide. Incertain embodiments, R⁵ of an acrylamide represented by Formula (II) mayinclude, but is not limited to, an unsaturated fatty alkyl moietycomprising either a mono- or poly unsaturated fatty alkyl moiety, suchas di-, tri, tetra, penta, or hexa-unsaturated fatty alkyl moiety. Incertain embodiments, the unsaturated fatty alkyl moiety may comprise:myristoleyl, palmitoleyl, sapienyl, oleyl, elaidyl, vaccenyl, linoleyl,linoelaidyl, α-linolenyl, arachidonyl, eicosapentaenoyl, erucyl, ordocosahexaenoyl moiety.

In certain embodiments, R⁵ of the acrylamide represented by Formula (II)may include, but is not limited to, a —C₆ or greater alkyl-(O—C₁₋₆alkyl)_(n), or C₆ or greater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein the —C₆or greater alkyl may be C₆₋₁₂ alkyl, C₁₁₋₂₀ alkyl, C₁₈₋₃₀ alkyl, orC₂₀₋₄₀ alkyl; wherein the —C₆ or greater alkenyl may be C₆₋₁₂ alkenyl,C₁₁₋₂₀ alkenyl, C₁₈₋₃₀ alkenyl, or C₂₀₋₄₀ alkenyl; wherein each alkylportion independently may be branched or unbranched, linear or cyclic,saturated or unsaturated, and may be optionally substituted with one ormore halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol); whereineach alkenyl portion independently may be branched or unbranched, linearor cyclic, mono- or poly-unsaturated, conjugated or unconjugated, andmay be optionally substituted with one or more halogens, C₁₋₆ alkoxygroups, or poly(ethylene glycol).

In certain embodiments, R⁶ may independently represent hydrogen; C₁₋₁₈alkyl or —C₁₋₁₈ alkyl-(O—C₁₋₆ alkyl)_(n), wherein the C₁₋₁₈ alkyl maybe, for example, methyl, ethyl, C₁₋₁₀ alkyl, C₃₋₁₈ alkyl, C₃₋₆ alkyl,C₆₋₁₂ alkyl, or C₁₂₋₁₈ alkyl; and wherein each alkyl portionindependently may be branched or unbranched, linear or cyclic, saturatedor unsaturated, and may be optionally substituted with one or morehalogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol); or is R⁴, or isR⁵.

In certain embodiments, the R⁷ moiety of Formula (III) may include, butis not limited to, a C₁₃ or greater alkyl moiety, such as a C₁₃₋₄₀alkyl; C₁₄ or greater alkyl; C₁₆ or greater alkyl; C₁₈ or greater alkyl;or C₂₀ or greater alkyl moiety. For example, the R⁷ moiety of Formula(III) may include, but is not limited to, a 10-undecenyl, lauryl,tridecyl, hexadecyl, stearyl, behenyl, lignoceryl, ceryl (heptacosanyl),montanyl, nonacosanyl, myricyl, dotriacontanyl, geddyl, or cetostearylmoiety.

In certain embodiments, the R⁷ moiety of Formula (III) may include, butis not limited to, a C₆ or greater alkenyl moiety, such as C₆₋₄₀alkenyl; C₈ or greater alkenyl; C₁₀ or greater alkenyl; C₁₂ or greateralkenyl; C₁₄ or greater alkenyl; C₁₈ or greater alkenyl; or C₂₀ orgreater alkenyl moiety. The R⁷ moiety of Formula (III) may include anunsaturated fatty alkyl moiety comprising either a mono- or polyunsaturated fatty alkyl moiety, such as di-, tri, tetra, penta, orhexa-unsaturated fatty alkyl moiety. In certain embodiments, theunsaturated fatty alkyl moiety may comprise: myristoleyl, palmitoleyl,sapienyl, oleyl, elaidyl, vaccenyl, linoleyl, linoelaidyl, α-linolenyl,arachidonyl, eicosapentaenoyl, erucyl, or docosahexaenoyl moiety.

In certain embodiments, R⁷ moiety of Formula (III) may include, but isnot limited to, a —C₆ or greater alkyl-(O—C₁₋₆ alkyl)_(n), or C₆ orgreater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein the —C₆ or greater alkyl maybe C₆₋₁₂ alkyl, C₁₁₋₂₀ alkyl, C₁₈₋₃₀ alkyl, or C₂₀₋₄₀ alkyl; wherein the—C₆ or greater alkenyl may be C₆₋₁₂ alkenyl, C₁₁₋₂₀ alkenyl, C₁₈₋₃₀alkenyl, or C₂₀₋₄₀ alkenyl; wherein each alkyl portion independently maybe branched or unbranched, linear or cyclic, saturated or unsaturated,and may be optionally substituted with one or more halogens, C₁₋₆ alkoxygroups, or poly(ethylene glycol); wherein each alkenyl portionindependently may be branched or unbranched, linear or cyclic, mono- orpoly-unsaturated, conjugated or unconjugated, and may be optionallysubstituted with one or more halogens, C₁₋₆ alkoxy groups, orpoly(ethylene glycol).

In certain embodiments, the vinyl ether represented by Formula (IV) mayinclude, but is not limited to, a C₂ or greater alkyl vinyl ether, C₂₋₄₀alkyl vinyl ether; C₆ or greater alkyl vinyl ether; C₁₂ or greater alkylvinyl ether; C₁₈ or greater alkyl vinyl ether; C₃ or greater alkenylvinyl ether; C₄ or greater alkenyl vinyl ether; C₆ or greater alkenylvinyl ether, C₆₋₄₀ alkenyl vinyl ether, C₈ or greater alkenyl vinylether, C₁₀ or greater alkenyl vinyl ether; C₁₂ or greater alkenyl vinylether, C₁₄ or greater alkenyl vinyl ether; or C₁₈ or greater alkenylvinyl ether. In certain embodiments, R⁸ of the vinyl ether representedby Formula (IV) may include, but is not limited to, a saturated fattyalkyl moiety, such as a tridecyl, isotridecyl, myristyl, pentadecyl,cetyl, palmityl, heptadecyl, stearyl, nonadecyl, arachidyl, heneicosyl,behenyl, lignoceryl, ceryl (heptacosanyl), montanyl, nonacosanyl,myricyl, dotriacontanyl, geddyl, or cetostearyl moiety. In certainembodiments, R⁸ of the vinyl ether represented by Formula (IV) mayinclude, but is not limited to, an unsaturated fatty alkyl moietycomprising either a mono- or poly unsaturated fatty alkyl moiety, suchas di-, tri, tetra, penta, or hexa-unsaturated fatty alkyl moiety. Incertain embodiments, the unsaturated fatty alkyl moiety may comprise:myristoleyl, palmitoleyl, sapienyl, oleyl, elaidyl, vaccenyl, linoleyl,linoelaidyl, α-linolenyl, arachidonyl, eicosapentaenoyl, erucyl, ordocosahexaenoyl moiety.

In certain embodiments, R⁸ of the vinyl ether represented by Formula(IV) may include, but is not limited to, a —C₂ or greater alkyl-(O—C₁₋₆alkyl)_(n), or C₃ or greater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein the —C₂or greater alkyl may be C₂₋₆ alkyl, C₆₋₁₂ alkyl, C₁₁₋₂₀ alkyl, C₁₈₋₃₀alkyl, or C₂₀₋₄₀ alkyl; wherein the —C₃ or greater alkenyl may be C₃₋₆alkenyl C₆₋₁₂ alkenyl, C₁₁₋₂₀ alkenyl, C₁₈₋₃₀ alkenyl, or C₂₀₋₄₀alkenyl; wherein each alkyl portion independently may be branched orunbranched, linear or cyclic, saturated or unsaturated, and may beoptionally substituted with one or more halogens, C₁₋₆ alkoxy groups, orpoly(ethylene glycol); wherein each alkenyl portion independently may bebranched or unbranched, linear or cyclic, mono- or poly-unsaturated,conjugated or unconjugated, and may be optionally substituted with oneor more halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol).

In certain embodiments, the surfactant-system thickening monomerrepresented by Formula (V) may include, but is not limited to, C₁ orgreater alkyl allyl ether; C₁₋₄₀ alkyl allyl ether; C₄ or greater alkylallyl ether; C₆ or greater alkyl allyl ether; C₈ or greater alkyl allylether; C₁₀ or greater alkyl allyl ether; C₁₂ or greater alkyl allylether; C₁₈ or greater alkyl allyl ether; C₃ or greater alkenyl allylether; C₆ or greater alkenyl allyl ether; C₈ or greater alkenyl allylether; C₁₀ or greater alkenyl allyl ether; C₁₂ or greater alkenyl allylether; C₁₄ or greater alkenyl allyl ether; or C₁₈ or greater alkenylallyl ether. In certain embodiments, R⁹ of the surfactant-systemthickening monomer represented by Formula (V) may include, but is notlimited to, a saturated fatty alkyl moiety, such as a tridecyl,isotridecyl, myristyl, pentadecyl, cetyl, palmityl, heptadecyl, stearyl,nonadecyl, arachidyl, heneicosyl, behenyl, lignoceryl, ceryl(heptacosanyl), montanyl, nonacosanyl, myricyl, dotriacontanyl, geddyl,or cetostearyl moiety. In certain embodiments, R⁹ of thesurfactant-system thickening monomer represented by Formula (V) mayinclude, but is not limited to, an unsaturated fatty alkyl moietycomprising either a mono- or poly unsaturated fatty alkyl moiety, suchas di-, tri, tetra, penta, or hexa-unsaturated fatty alkyl moiety. Incertain embodiments, the unsaturated fatty alkyl moiety may comprise:myristoleyl, palmitoleyl, sapienyl, oleyl, elaidyl, vaccenyl, linoleyl,linoelaidyl, α-linolenyl, arachidonyl, eicosapentaenoyl, erucyl, ordocosahexaenoyl moiety.

In certain embodiments, R⁹ of the surfactant-system thickening monomerrepresented by Formula (V) may include, but is not limited to, a —C orgreater alkyl-(O—C₁₋₆ alkyl)_(n), or C₃ or greater alkenyl-(O—C₁₋₆alkyl)_(n); wherein the —C₁ or greater alkyl may be C₁₋₆ alkyl, C₆₋₁₂alkyl, C₁₁₋₂₀ alkyl, C₁₈₋₃₀ alkyl, or C₂₀₋₄₀ alkyl; wherein the —C₃ orgreater alkenyl may be C₃₋₆ alkenyl C₆₋₁₂ alkenyl, C₁₁₋₂₀ alkenyl,C₁₈₋₃₀ alkenyl, or C₂₀₋₄₀ alkenyl; wherein each alkyl portionindependently may be branched or unbranched, linear or cyclic, saturatedor unsaturated, and may be optionally substituted with one or morehalogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol); wherein eachalkenyl portion independently may be branched or unbranched, linear orcyclic, mono- or poly-unsaturated, conjugated or unconjugated, and maybe optionally substituted with one or more halogens, C₁₋₆ alkoxy groups,or poly(ethylene glycol).

In certain embodiments, the variable R⁴, R⁵, R⁷, R⁸, or R⁹ of thesurfactant-system thickening monomer to be employed in the preparationof the surfactant-system thickening polymeric segment P2, optionallywith L¹, L², or L¹ and L², may be independently derived or prepared fromthe hydrophobic portion of a surfactant, the hydrophobic portion of alipid, or the hydrophobic portion of a fatty alcohol. For example,selection of the variable R⁴, R⁵, R⁷, R⁸, or R⁹, optionally with L¹, L²,or L¹ and L², may be determined by the particular surfactant mixture,solution, or system to be thickened by the surfactable-compatible starmacromolecule or polymer. In certain embodiments, the hydrophobicportion of the surfactant that is included in the particular surfactantmixture, solution, or system to be thickened may be selected as thevariable R⁴, R⁵, R⁷, R⁸, or R⁹ of Formulas (I)-(V) for the one or moreof the surfactant-compatible-enhancing monomers to be employed inpreparing the surfactant-compatible-enhancing polymeric segment P2.

In certain embodiments, the variable L² may independently represent(CH₂)₁₋₄₀, such as (CH₂)₁₋₁₀, (CH₂)₁₀₋₂₀, (CH₂)₁₈₋₃₀, (CH₂)₂₀₋₄₀,(CH₂)₁₋₄, (CH₂)₃₋₈, or (CH₂)₅₋₁₀; C₁₋₄₀ alkyl, such as C₁₋₄₀ alkyl,C₁₀₋₂₀ alkyl, C₁₈₋₃₀ alkyl, C₂₀₋₄₀ alkyl, C₁₋₄ alkyl, C₃₋₈ alkyl, orC₅₋₁₀ alkyl; (O—C₂₋₆ alkyl)_(n); or (C₂₋₆ alkyl)-(O—C₂₋₆ alkyl)_(n);wherein the alkyl may be branched or unbranched, linear or cyclic, andmay be optionally substituted with one or more halogens, C₁₋₆ alkoxygroups, or poly(ethylene glycol); and where n independently represents avalue in the range of 1-1000, such as a value in the range of 1-100,20-80, 50-500, 350-750, 200-400, or 600-1000.

In certain embodiments, suitable surfactant-system thickening monomersthat may be used to form a surfactant-system thickening polymericsegment, for example, to form polymeric segment P2, may include, but arenot limited to, poly(ethylene glycol) behenyl ether methacrylate;10-undecenyl methacrylate, lauryl acrylate, tridecyl acrylate, hexadecylacrylate, stearyl acrylate, behenyl acrylate, lauryl methacrylate,tridecyl methacrylate, hexadecyl methacrylate, stearyl methacrylate,behenyl methacrylate, lauryl ethacrylate, tridecyl ethacrylate,hexadecyl ethacrylate, stearyl ethacrylate, poly(propylene glycol)acrylate, poly(ethylene glycol) methyl ether acrylate, poly(propyleneglycol) 4-nonylphenyl ether acrylate, poly(ethylene glycol) phenyl etheracrylate, poly(propylene glycol) methyl ether acrylate, poly(ethyleneglycol) methacrylate, poly(ethylene glycol) methyl ether methacrylate,poly(ethylene glycol) behenyl ether methacrylate, N-octadecylacrylamide, N-dodecyl methacrylamide, styrene optionally substitutedwith one or more C₁-C₁₈ straight or branched chain alkyl groups; vinyldecanoate, vinyl neodecanoate, vinyl neononanoate, vinyl laurate, vinylstearate, allyl heptafluorobutyrate, allyl heptafluoroisopropyl ether,allyl 1H,1H-pentadecafluorooctyl ether, allylpentafluorobenzene, allylperfluoroheptanoate, allyl perfluorononanoate, allyl perfluorooctanoate,allyl tetrafluoroethyl ether, allyl trifluoroacetate,bis(hexafluoroisopropyl) itaconate, bis(hexafluoroisopropyl) maleate,bis(perfluorooctyl)itaconate, bis(perfluorooctyl)maleate,bis(trifluoroethyl) itaconate, bis(2,2,2-trifluoroethyl) maleate,2-(N-butylperfluorooctanesulfamido) ethyl acrylate,trihydroperfluoroheptyl acrylate, trihydroperfluoroheptyl methacrylate,trihydroperfluoroundecyl acrylate, trihydroperfluoroundecylmethacrylate, 2-(N-ethylperfluorooctane sulfamido) ethyl acrylate,2-(N-ethylperfluorooctane sulfamido) ethyl methacrylate, 2-fluoroethylacrylate, 2-fluoroethyl methacrylate, tetrahydroperfluorodecyl acrylate,tetrahydroperfluorodecyl methacrylate, 1H,1H-heptafluorobutylacrylamide,heptafluorobutyl acrylate, 1H,1H-heptafluorobutylmethacrylamide,1H,1H-heptafluoro-n-butyl methacrylate, 1H,1H,9H-hexadecafluorononylacrylate, 1H,1H,9H-hexadecafluorononyl methacrylate,2,2,3,4,4,4-hexafluorobutyl acrylate, 2,2,3,4,4,4-hexafluorobutylmethacrylate, 1H,1H,5H-octafluoropentyl acrylate,1H,1H,5H-octafluoropentyl methacrylate, pentafluorobenzyl acrylate,pentafluorobenzyl methacrylate, pentafluorophenyl acrylate,pentafluorophenyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate,2,2,3,3,3-pentafluoropropyl methacrylate,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl methacrylate,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-Heneicosafluorododecylmethacrylate, perfluorocyclohexyl-1,4-dimethyl dimethacrylate,perfluorocyclohexyl methyl acrylate, perfluorocyclohexylmethylmethacrylate, perfluorocyclopentene, perfluoroheptoxypoly(propyloxy)acrylate, perfluoroheptoxypoly-(propyloxy) methacrylate,perfluorooctoxy-poly(iso-butoxy)-2-chloropropoxy-1,2-propyl diacrylate,mono-perfluorooctyl maleate, mono-perfluorooctyl itaconate,perfluorooctyl acrylate, 1H,1H-perfluorooctyl acrylate,1H,1H-perfluorooctyl methacrylate, polyperfluoroethylene glycoldiacrylate, polyperfluoroethylene glycol dimethacrylate,2,2,3,3-tetrafluoro-1,4-butanediol diacrylate,2,2,3,3-tetrafluoro-1,4-butanediol dimethacrylate,2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3-tetrafluoropropylmethacrylate, 1,1,5,5-tetrahydroperfluoro-1,5-pentanedioldimethacrylate, trifluoroethyl acid itaconate, mono-trifluoroethyl acidmaleate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethylmethacrylate, 3-(trifluoromethyl) benzyl acrylate, 3-(trifluoromethyl)benzyl methacrylate, 1-(trifluoromethyl) vinyl acetate, 4-vinylbenzylhexafluoroisopropyl ether, 4-vinylbenzyl perfluorooctanoate, vinylheptafluorobutyrate, vinyl perfluoroheptanoate, vinylperfluorononanoate, vinyl perfluorooctanoate, vinyl trifluoroacetate,hexafluoroisopropyl itaconate, hexafluoroisopropyl methacrylate andmixtures thereof.

In certain embodiments, a suitable surfactant-system thickeningpolymeric segment, such as P2 or a further segment, may include aportion represented by Formula E:

wherein:

-   -   R¹¹, R¹², R¹³ independently represent hydrogen, methyl, ethyl,        or C₃₋₁₈ alkyl, for example C₃₋₆ alkyl, C₆₋₁₂ alkyl, or C₁₂₋₁₈        alkyl; wherein the alkyl may be branched or unbranched, linear        or cyclic, and may be optionally substituted with one or more        halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol);    -   R¹⁴ independently represents C₁₋₁₂ hydrocarbyl, —C₁₋₁₂        hydrocarbyl-(O—C₁₋₆ hydrocarbyl)_(w), —C₁₋₁₂        hydrocarbyl-((CO)O—C₁₋₆ hydrocarbyl)_(w), —C₁₋₁₂        hydrocarbyl-((CO)NH—C₁₋₆ hydrocarbyl)_(w); wherein each        hydrocarbyl portion independently may be branched or unbranched,        linear or cyclic, saturated (alkyl) or unsaturated (alkenyl),        and may be optionally substituted with one or more halogens,        C₁₋₆ alkoxy groups, or poly(ethylene glycol);    -   R¹⁵ independently represents C₁₃₋₄₀ hydrocarbyl, —C₁₃₋₄₀        hydrocarbyl-(O—C₁₋₆ hydrocarbyl)_(w), —C₁₃₋₄₀        hydrocarbyl-((CO)O—C₁₋₆ hydrocarbyl)_(w), C₁₃₋₄₀        hydrocarbyl-((CO)NH—C₁₋₆ alkyl)_(w); wherein each hydrocarbyl        portion independently may be branched or unbranched, linear or        cyclic, saturated (alkyl) or unsaturated (alkenyl), and may be        optionally substituted with one or more halogens, C₁₋₆ alkoxy        groups, or poly(ethylene glycol); or a hydrophobic moiety of a        surfactant, a hydrophobic moiety of a lipid, or a hydrophobic        moiety of a fatty alcohol;    -   Y represents a covalent bond, ethylene glycol, poly(ethylene        glycol), polyether, polyamide, C₁₋₆ alkyl, or combinations        thereof, or is independently absent;    -   m independently represents a value in the range of 1-500;    -   n independently represents a value in the range of 1-500; and    -   w independently represents a value in the range of 1-1000.

In certain embodiments, R¹¹, R¹², and R¹³ in the portion represented byFormula E may independently represent hydrogen, methyl, ethyl, or C₃₋₁₈alkyl, for example C₃₋₆ alkyl, C₆₋₁₂ alkyl, or C₁₂₋₁₈ alkyl; wherein thealkyl may be branched or unbranched, linear or cyclic. In certainembodiments, R¹¹, R¹², and R¹³ may independently represent hydrogen ormethyl. In certain embodiments, R¹¹, R¹², and R¹³ may independentlyrepresent C₃₋₆ alkyl, C₆₋₁₂ alkyl, or C₁₂₋₁₈ alkyl; wherein the alkylmay be branched or unbranched, linear or cyclic, and may be optionallysubstituted with one or more halogens, C₁₋₆ alkoxy groups, orpoly(ethylene glycol).

In certain embodiments, R¹⁴ in the portion represented by Formula E mayindependently represent C₁₋₁₂ hydrocarbyl, —C₁₋₁₂ hydrocarbyl-(O—C₁₋₆hydrocarbyl)_(w), —C₁₋₁₂ hydrocarbyl-((CO)O—C₁₋₆ hydrocarbyl)_(w),—C₁₋₁₂ hydrocarbyl-((CO)NH—C₁₋₆ hydrocarbyl)_(w); wherein the C₁₋₁₂hydrocarbyl portion may represent C₁₋₁₂ alkyl, for example, methyl,ethyl, C₃₋₁₂ alkyl, C₃₋₆ alkyl, C₆₋₁₂ alkyl, or C₄₋₈ alkyl, or mayrepresent C₃₋₁₂ alkenyl, for example, C₃₋₆ alkenyl, C₆₋₁₂ alkenyl, orC₄₋₈ alkenyl; wherein the C₁₋₆ hydrocarbyl portion may represent C₁₋₆alkyl, for example, methyl, ethyl, or C₃₋₆ alkyl, or may represent C₃₋₆alkenyl, for example, C₄₋₆ alkenyl; wherein the alkyl may be branched orunbranched, linear or cyclic, and may be optionally substituted with oneor more halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol); whereinthe alkenyl portion independently may be branched or unbranched, linearor cyclic, mono- or poly-unsaturated, conjugated or unconjugated, andmay be optionally substituted with one or more halogens, C₁₋₆ alkoxygroups, or poly(ethylene glycol); and wherein w independently representsa value in the range of 1-1000, such as a value in the range of 1-100,20-80, 50-500, 350-750, 200-400, or 600-1000.

In certain embodiments, R¹⁵ in the portion represented by Formula E mayindependently represent C₁₃₋₄₀ hydrocarbyl, —C₁₃₋₄₀ hydrocarbyl-(O—C₁₋₆hydrocarbyl)_(w), —C₁₃₋₄₀ hydrocarbyl-((CO)O—C₁₋₆ hydrocarbyl)_(w),C₁₃₋₄₀ hydrocarbyl-((CO)NH—C₁₋₆ alkyl)_(w); wherein the C₁₃₋₄₀hydrocarbyl portion may represent C₁₃₋₄₀ alkyl, for example, C₁₃₋₁₈alkyl, C₁₃₋₂₀ alkyl, C₁₈₋₃₀ alkyl, or C₃₀₋₄₀ alkyl, or may representC₁₃₋₄₀ alkenyl, for example, C₁₃₋₁₈ alkenyl, C₁₃₋₂₀ alkenyl, C₁₈₋₃₀alkenyl, or C₃₀₋₄₀ alkenyl; wherein the C₁₋₆ hydrocarbyl portion mayrepresent C₁₋₆ alkyl, for example, methyl, ethyl, or C₃₋₆ alkyl, or mayrepresent C₃₋₆ alkenyl, for example, C₄₋₆ alkenyl; wherein the alkyl maybe branched or unbranched, linear or cyclic, and may be optionallysubstituted with one or more halogens, C₁₋₆ alkoxy groups, orpoly(ethylene glycol); wherein the alkenyl portion independently may bebranched or unbranched, linear or cyclic, mono- or poly-unsaturated,conjugated or unconjugated, and may be optionally substituted with oneor more halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol); andwherein w independently represents a value in the range of 1-1000, suchas a value in the range of 1-100, 20-80, 50-500, 350-750, 200-400, or600-1000.

In certain embodiments, the variable m in the portion represented byFormula E independently represents a value in the range of 1-500, suchas a value in the range of 1-100, 20-80, 50-500, 350-500, 200-400, or100-250.

In certain embodiments, the variable n in the portion represented byFormula E independently represents a value in the range of 1-500, suchas a value in the range of 1-100, 20-80, 50-500, 350-500, 200-400, or100-250.

Suitable star macromolecules may comprise polymeric arms that are of thesame type or a different type and are homopolymeric, copolymeric,comprise multiple block segments, comprise multiple blocky segments,random segments, gradient segments, or no particular segments. Incertain embodiments, the star macromolecule may comprise, for example,one or more arm-types, such as, two or more, three or more, four ormore, or five or more arm-types. Suitable arm types may include, but arenot limited to, homopolymeric arms, copolymeric arms, such as randomcopolymeric arms, block copolymeric arms, or blocky copolymeric arms, orcombinations thereof. For example, a star macromolecule may comprisehomopolymeric arms and copolymeric arms, such as block copolymeric arms.Suitable arm types may also include, but are not limited to,surfactant-system thickening arms, hydrophilic arms, hydrophobic arms,micelle-philic arms, or amphiphilic arms. In certain embodiments, a starmacromolecule arm may comprise hydrophilic polymeric segments comprisinghydrophilic monomeric residues, surfactant-system thickening segmentscomprising surfactant-system thickening monomeric residues,micelle-philic segments comprising micelle-philic monomeric residues,hydrophobic polymeric segments comprising hydrophobic monomericresidues, amphiphilic polymeric segments comprising amphiphilicmonomeric residues, or combinations thereof. For example, in certainembodiments, a star macromolecule may comprise homopolymeric arms andcopolymeric arms, such as hydrophilic homopolymeric arms, copolymericarms comprising hydrophilic polymeric segments and surfactant-systemthickening polymeric segments, and copolymeric arms comprisinghydrophilic polymeric segments and hydrophobic polymeric segments.

Suitable star macromolecules may comprise hydrophilic polymericsegments, such as P1, P3, or P5, which may comprise a hydrophilichomopolymeric segment or a hydrophilic copolymeric segment comprisingrepeat units of monomeric residues of one or more, such as two or more,polymerized hydrophilic monomers, for example, a hydrophilic segmentblock copolymeric segment, a hydrophilic segment blocky copolymericsegment, a hydrophilic gradient copolymeric segment, or a hydrophilicrandom copolymeric segment.

Suitable star macromolecules may comprise surfactant-system thickeningpolymeric segments, such as P2, which may comprise a surfactant-systemthickening homopolymerized segment or a surfactant-system thickeningcopolymerized segment comprising repeat units of monomeric residues ofone or more, such as two or more, polymerized surfactant-systemthickening monomers, and optionally, monomeric residues of one or more,such as two or more, polymerized hydrophobic or hydrophilic monomers.The surfactant-system thickening copolymerized segment may be asurfactant-system thickening segment block copolymeric segment, asurfactant-system thickening gradient copolymeric segment, or asurfactant-system thickening random copolymeric segment. In certainembodiments, the monomeric residues of the one or more, or two or more,polymerized hydrophobic or hydrophilic monomers are present in thesurfactant-system thickening copolymeric segment. For example, thesurfactant-system thickening copolymerized segment may be block, blocky,gradient, or random copolymeric segment comprising repeat units ofmonomeric residues of one or more, such as two or more, polymerizedsurfactant-system thickening monomers, and monomeric residues of one ormore, such as two or more, polymerized hydrophobic monomers. Forexample, the surfactant-system thickening copolymerized segment may beblock, blocky, gradient, or random copolymeric segment comprising repeatunits of monomeric residues of one or more, such as two or more,polymerized surfactant-system thickening monomers, and monomericresidues of one or more, such as two or more, polymerized hydrophilicmonomers. In certain embodiments, the surfactant-system thickeningcopolymerized segment may be block, blocky, gradient, or randomcopolymeric segment comprising repeat units of monomeric residues of oneor more, such as two or more, polymerized surfactant-system thickeningmonomers, and monomeric residues of one or more, such as two or more,polymerized hydrophobic monomers, and monomeric residues of one or more,such as two or more, polymerized hydrophilic monomers.

Suitable star macromolecules may comprise hydrophobic polymericsegments, such as P4, which may comprise a hydrophobic homopolymericsegment or a hydrophobic copolymeric segment comprising repeat units ofmonomeric residues of one or more, such as two or more, polymerizedhydrophobic monomers, for example, a hydrophobic segment blockcopolymeric segment, a hydrophobic segment blocky copolymeric segment, ahydrophobic gradient copolymeric segment, or a hydrophobic randomcopolymeric segment.

Suitable star macromolecules may comprise arms, for example, polymericarms, covalently linked to the core of the star macromolecule. Incertain embodiments, the arms of a star macromolecule may be covalentlylinked to the core of the star macromolecule via crosslinking, such ascrosslinking with a crosslinker, for example, a hydrophobic difunctionalcrosslinker or a hydrophilic difunctional crosslinker. For example, armsof a star macromolecule, such as homopolymeric arms and block or blockycopolymeric arms of a mikto star macromolecule, may be covalently linkedtogether to form a core by crosslinking an end of the arms with acrosslinker, such as with a hydrophobic difunctional crosslinker or ahydrophilic difunctional crosslinker.

Suitable star macromolecules may comprise arms of varying length and/ordegree of polymerization. In certain embodiments, for example, a starmacromolecule may comprise homopolymeric arms and block or blockycopolymeric arms, wherein the homopolymeric arms of a shorter lengthand/or a lesser degree of polymerization in relation to the block orblocky copolymeric arms. In certain embodiments, for example, a starmacromolecule may comprise homopolymeric arms and block copolymericarms, wherein the block or blocky copolymeric arms of a longer lengthand/or a greater degree of polymerization in relation to thehomopolymeric arms. In certain embodiments, a star macromolecule maycomprise hydrophilic homopolymeric arms and block copolymeric arms,comprising (i) hydrophobic polymeric segments distal to the star coreand hydrophilic polymeric segments that are proximal to the core of thestar, wherein a distal portion of the hydrophobic polymeric segments ofthe copolymeric arm extends beyond a distal portion of the hydrophilichomopolymeric arms, and (ii) surfactant-system thickening polymericsegments distal to the star core and hydrophilic polymeric segments thatare proximal to the core of the star, wherein a distal portion of thesurfactant-system thickening polymeric segments of the copolymeric armextends beyond a distal portion of the hydrophilic homopolymeric arms.For example, a star macromolecule may comprise hydrophilic homopolymericarms comprising polymerized hydrophilic monomeric residues and blockcopolymeric arms comprising (i) hydrophobic polymeric segments distal tothe core of the star and hydrophilic polymeric segments that areproximal to the core of the star, wherein the distal hydrophobicpolymeric segments extend beyond the most distal portion, in relation tothe core, of the hydrophilic homopolymeric arms, and/or wherein a distalportion of the proximal hydrophilic polymeric segments of thecopolymeric arm extend beyond the most distal portion, in relation tothe core, of the hydrophilic homopolymeric arms, (ii) surfactant-systemthickening polymeric segments distal to the core of the star andhydrophilic polymeric segments that are proximal to the core of thestar, wherein the distal surfactant-system thickening polymeric segmentsextend beyond the most distal portion, in relation to the core, of thehydrophilic homopolymeric arms, and/or wherein a distal portion of theproximal hydrophilic polymeric segments of the copolymeric arm extendbeyond the most distal portion, in relation to the core, of thehydrophilic homopolymeric arms.

In certain embodiments, a star macromolecule may comprise hydrophilichomopolymeric arms and block or blocky copolymeric arms, comprising (i)hydrophobic polymeric segments distal to the star core and hydrophilicpolymeric segments that are proximal to the star core, wherein thedegree of polymerization of the hydrophilic polymeric segments of thecopolymeric arms are greater than, for example, greater than 20%, suchas between 30% to 300%, between 40% to 250%, between 50% to 200%,between 75% to 250%, or between 100% to 500%, the degree ofpolymerization of the hydrophilic homopolymeric arms, such that a distalportion of the hydrophilic polymeric segments of the copolymeric armextends beyond the a distal portion of the hydrophilic homopolymericarms, and (ii) surfactant-system thickening polymeric segments distal tothe star core and hydrophilic polymeric segments that are proximal tothe star core, wherein the degree of polymerization of the hydrophilicpolymeric segments of the copolymeric arms are greater than, forexample, greater than 20%, such as between 30% to 300%, between 40% to250%, between 50% to 200%, between 75% to 250%, or between 100% to 500%,the degree of polymerization of the hydrophilic homopolymeric arms, suchthat a distal portion of the hydrophilic polymeric segments of thecopolymeric arms extends beyond the a distal portion of the hydrophilichomopolymeric arms.

In certain embodiments, a suitable star macromolecules may comprise acore and a plurality of polymeric arms, wherein the plurality ofpolymeric arms comprises: (i) at least a first polymeric arm comprisinga hydrophilic polymeric segment, (ii) at least a second polymeric armcomprising a surfactant-system thickening polymeric segment distal tothe core of the star and a hydrophilic polymeric segment proximal to thecore of the star, and optionally (iii) at least a third polymeric armcomprising a hydrophobic polymeric segment distal to the core of thestar and a hydrophilic polymeric segment proximal to the core of thestar. One or more of the plurality of polymeric arms may behomopolymeric, copolymeric, block copolymeric, blocky copolymeric,gradient copolymeric, or random copolymeric polymeric arms, and may havethe same or different degrees of polymerization. One or more of thepolymeric segments within the plurality of polymeric arms may behomopolymeric, copolymeric, block copolymeric, blocky copolymeric,gradient copolymeric, or random copolymeric polymeric segments, and mayhave the same or different degrees of polymerization.

In certain embodiments, the hydrophilic polymeric segment of the atleast first polymeric arm may be comprised of a plurality of monomericresidues of polymerized hydrophilic monomers, wherein the hydrophilicpolymeric segment may have the same or different degree ofpolymerization and may be comprised of in the range of between 5 to 2000monomeric residues of polymerized hydrophilic monomers, such as between10 to 2000; between 50 to 500; between 50 to 400; between 50 to 300;between 50 to 200; between 100 to 250; between 125 to 175; between 150to 300; between 300 to 800; between 400 to 800; between 500 to 800;between 600 to 800; between 600 to 1000; between 800 to 1500; between1000 to 2000; between 1500 to 2000; or between 550 to 1000 monomericresidues.

In certain embodiments, the surfactant-system thickening polymericsegment of the at least second polymeric arm may be comprised of aplurality of monomeric residues of polymerized surfactant-systemthickening monomers, wherein the surfactant-system thickening polymericsegment may have the same or different degree of polymerization and maybe comprised of in the range of between 1 to 500 monomeric residues ofpolymerized surfactant-system thickening monomers, such as between 1 to450; between 1 to 400; between 1 to 350; between 10 to 425; between 10to 500; between 10 to 400; between 10 to 300; between 10 to 200; between10 to 100; between 10 to 75; between 10 to 50; between 10 to 40; between10 to 30; between 10 to 20; between 10 to 15; between 15 to 25; between20 to 30; between 20 to 40; between 20 to 50; between 20 to 250; between30 to 200; between 50 to 200; between 50 to 100; between 200 to 400;between 150 to 300; between 300 to 500; between 250 to 450; between 50to 150; between 1 to 10; between 5 to 15; between 7 to 30; between 1 to60; between 1 to 50; between 1 to 45; between 5 to 40; between 8 to 35;between 10 to 30; between 12 to 25; between 14 to 22; between 15 to 30;between 17 to 35; or between 5 to 20 monomeric residues. In certainembodiments, the hydrophilic polymeric segment of the at least secondpolymeric arm may be comprised of a plurality of monomeric residues ofpolymerized hydrophilic monomers, wherein the hydrophilic polymericsegment may have the same or different degree of polymerization and maybe comprised of in the range of between 10 to 5000 monomeric residues ofpolymerized hydrophilic monomers, such as between 10 to 4000; between 10to 3000; between 10 to 2000; between 10 to 1000; between 10 to 500;between 50 to 500; between 50 to 400; between 50 to 300; between 50 to200; between 100 to 250; between 125 to 175; between 150 to 300; between300 to 800; between 400 to 800; between 500 to 800; between 600 to 800;between 600 to 1000; between 800 to 1500; between 1000 to 2000; between1500 to 2000; between 2000 to 5000; between 2500 to 4500; between 3000to 5000; or between 550 to 1000 monomeric residues.

In certain embodiments, the hydrophobic polymeric segment of the atleast third polymeric arm may be comprised of a plurality of monomericresidues of polymerized hydrophobic monomers, wherein thesurfactant-system thickening polymeric segment may have the same ordifferent degree of polymerization and may be comprised of in the rangeof between 1 to 500 monomeric residues of polymerized hydrophobicmonomers, such as between 1 to 450; between 1 to 400; between 1 to 350;between 10 to 425; between 10 to 500; between 10 to 400; between 10 to300; between 10 to 200; between 10 to 100; between 10 to 75; between 10to 50; between 10 to 40; between 10 to 30; between 10 to 20; between 10to 15; between 15 to 25; between 20 to 30; between 20 to 40; between 20to 50; between 20 to 250; between 30 to 200; between 50 to 200; between50 to 100; between 200 to 400; between 150 to 300; between 300 to 500;between 250 to 450; between 50 to 150; between 1 to 10; between 5 to 15;between 7 to 30; between 1 to 60; between 1 to 50; between 1 to 45;between 5 to 40; between 8 to 35; between 10 to 30; between 12 to 25;between 14 to 22; between 15 to 30; between 17 to 35; or between 5 to 20monomeric residues. In certain embodiments, the hydrophilic polymericsegment of the at least third polymeric arm may be comprised of aplurality of monomeric residues of polymerized hydrophilic monomers,wherein the hydrophilic polymeric segment may have the same or differentdegree of polymerization and may be comprised of in the range of between10 to 5000 monomeric residues of polymerized hydrophilic monomers, suchas between 10 to 4000; between 10 to 3000; between 10 to 2000; between10 to 1000; between 10 to 500; between 50 to 500; between 50 to 400;between 50 to 300; between 50 to 200; between 100 to 250; between 125 to175; between 150 to 300; between 300 to 800; between 400 to 800; between500 to 800; between 600 to 800; between 600 to 1000; between 800 to1500; between 1000 to 2000; between 1500 to 2000; between 2000 to 5000;between 2500 to 4500; between 3000 to 5000; or between 550 to 1000monomeric residues.

In certain embodiments, the polymeric segment may comprise in the rangeof between 5-100% of the monomeric residues of one or more polymerizedmonomers, for example, between 5-95%, such as between 5-90%; between5-80%; between 5-75%; between 5-70%; between 5-60%; between 5-50%;between 5-40%; between 5-35%; between 5-30%; between 5-25%; between5-20%; between 5-15%; between 5-10%; between 25-75%; between 50-100%;between 35-65%; or between 10-40% of the monomeric residues of one ormore polymerized monomers.

In certain embodiments, the number of monomeric residues in P1 of asuitable star macromolecule may be represented by q1, and may have avalue in the range of between 5 to 2000 monomeric residues, such asbetween 10 to 2000; between 50 to 500; between 50 to 400; between 50 to300; between 50 to 200; between 100 to 250; between 125 to 175; between150 to 300; between 300 to 800; between 400 to 800; between 500 to 800;between 600 to 800; between 600 to 1000; between 800 to 1500; between1000 to 2000; between 1500 to 2000; or between 550 to 1000 monomericresidues.

In certain embodiments, the number of monomeric residues in P2 of asuitable star macromolecule may be represented by q2, and may have avalue in the range of between 1 to 500 monomeric residues, such asbetween 1 to 450; between 1 to 400; between 1 to 350; between 10 to 425;between 10 to 500; between 10 to 400; between 10 to 300; between 10 to200; between 10 to 100; between 10 to 75; between 10 to 50; between 10to 40; between 10 to 30; between 10 to 20; between 10 to 15; between 15to 25; between 20 to 30; between 20 to 40; between 20 to 50; between 20to 250; between 30 to 200; between 50 to 200; between 50 to 100; between200 to 400; between 150 to 300; between 300 to 500; between 250 to 450;between 50 to 150; between 1 to 10; between 5 to 15; between 7 to 30;between 1 to 60; between 1 to 50; between 1 to 45; between 5 to 40;between 8 to 35; between 10 to 30; between 12 to 25; between 14 to 22;between 15 to 30; between 17 to 35; or between 5 to 20 monomericresidues.

In certain embodiments, the number of monomeric residues in P3 of asuitable star macromolecule may be represented by q3, and may have avalue in the range of between 10 to 5000 monomeric residues, such asbetween 10 to 4000; between 10 to 3000; between 10 to 2000; between 10to 1000; between 10 to 500; between 50 to 500; between 50 to 400;between 50 to 300; between 50 to 200; between 100 to 250; between 125 to175; between 150 to 300; between 300 to 800; between 400 to 800; between500 to 800; between 600 to 800; between 600 to 1000; between 800 to1500; between 1000 to 2000; between 1500 to 2000; between 2000 to 5000;between 2500 to 4500; between 3000 to 5000; or between 550 to 1000monomeric residues.

In certain embodiments, the number of monomeric residues in P4 of asuitable star macromolecule may be represented by q4, and may have avalue in the range of between 1 to 500 monomeric residues, such asbetween 1 to 450; between 1 to 400; between 1 to 350; between 5 to 500;between 5 to 300; between 5 to 100; between 10 to 425; between 10 to500; between 10 to 400; between 10 to 300; between 10 to 200; between 10to 100; between 10 to 75; between 10 to 50; between 10 to 40; between 10to 30; between 10 to 20; between 10 to 15; between 15 to 25; between 20to 30; between 20 to 40; between 20 to 50; between 20 to 250; between 30to 100; between 30 to 50; between 30 to 200; between 50 to 200; between50 to 100; between 200 to 400; between 150 to 300; between 300 to 500;between 250 to 450; between 50 to 150; between 1 to 10; between 5 to 15;between 7 to 30; between 1 to 60; between 1 to 50; between 1 to 45;between 5 to 40; between 8 to 35; between 10 to 30; between 12 to 25;between 14 to 22; between 15 to 30; between 17 to 35; or between 5 to 20monomeric residues.

In certain embodiments, the number of monomeric residues in P5 of asuitable star macromolecule may be represented by q5, and may have avalue in the range of between 10 to 5000 monomeric residues, such asbetween 10 to 4000; between 10 to 3000; between 10 to 2000; between 10to 1000; between 10 to 500; between 50 to 500; between 50 to 400;between 50 to 300; between 50 to 200; between 100 to 250; between 125 to175; between 150 to 300; between 300 to 800; between 400 to 800; between500 to 800; between 600 to 800; between 600 to 1000; between 800 to1500; between 1000 to 2000; between 1500 to 2000; between 2000 to 5000;between 2500 to 4500; between 3000 to 5000; or between 550 to 1000monomeric residues.

Suitable star macromolecules may have a wide range of total number ofarms, for example, a star macromolecule may comprise 5 arms or more. Forexample, a suitable star macromolecule may comprise a sum total ofpolymeric arms in the range of between 5 and 5000, such as between 10 to5000; between 10 to 4000; between 10 to 3000; between 10 to 2000;between 10 to 1000; between 10 to 500; between 10 and 400; between 12and 300; between 14 and 200; between 14 and 150; between 15 and 100;between 15 and 90; between 15 and 80; between 15 and 70; between 15 and60; between 15 and 50; between 20 and 50; between 25 and 45; between 25and 35; between 30 and 45; between 30 and 50; between 50 to 500; between50 to 400; between 50 to 300; between 50 to 200; between 100 to 250;between 125 to 175; between 150 to 300; between 300 to 800; between 400to 800; between 500 to 800; between 600 to 800; between 600 to 1000;between 800 to 1500; between 1000 to 2000; between 1500 to 2000; between2000 to 5000; between 2500 to 4500; between 3000 to 5000; or between 550to 1000 polymeric arms.

In certain embodiments, the at least first polymeric arms, for example,as provided in star macromolecules represented by Formulas A, B, C, orD, covalently attached to the core may be independently represented byr, and may have a value in the range of between 1 to 1000, such asbetween 2 and 1000; between 3 and 1000; between 4 and 1000; between 5and 1000; between 10 to 1000; between 10 to 500; between 10 and 400;between 2 and 500; between 3 and 300; between 4 and 200; between 5 and150; between 6 and 100; between 7 and 75; between 8 and 50; between 9and 40; between 10 and 30; between 20 and 30; between 20 and 40; between20 and 50; between 25 and 35; between 25 and 45; between 25 and 50;between 75 and 125; between 10 and 75; between 12 and 300; between 14and 200; between 14 and 150; between 15 and 100; between 15 and 90;between 15 and 80; between 15 and 70; between 15 and 60; between 15 and50; between 15 and 45; between 15 and 30; between 30 and 45; between 30and 50; between 50 to 500; between 50 to 400; between 50 to 300; between50 to 200; between 50 and 100; between 100 to 250; between 125 to 175;between 150 to 300; between 300 to 800; between 400 to 800; between 500to 800; between 600 to 800; between 600 to 1000.

In certain embodiments, the at least second polymeric arms, for example,as provided in star macromolecules represented by Formulas A, B, C, orD, covalently attached to the core may be independently represented bys, and may have a value in the range of between 1 to 1000, such asbetween 2 and 1000; between 3 and 1000; between 4 and 1000; between 5and 1000; between 10 to 1000; between 10 to 500; between 10 and 400;between 2 and 500; between 3 and 300; between 4 and 200; between 5 and150; between 6 and 100; between 7 and 75; between 8 and 50; between 9and 40; between 10 and 30; between 20 and 30; between 20 and 40; between20 and 50; between 25 and 35; between 25 and 45; between 25 and 50;between 75 and 125; between 10 and 75; between 12 and 300; between 14and 200; between 14 and 150; between 15 and 100; between 15 and 90;between 15 and 80; between 15 and 70; between 15 and 60; between 15 and50; between 15 and 45; between 15 and 30; between 30 and 45; between 30and 50; between 50 to 500; between 50 to 400; between 50 to 300; between50 to 200; between 50 and 100; between 100 to 250; between 125 to 175;between 150 to 300; between 300 to 800; between 400 to 800; between 500to 800; between 600 to 800; between 600 to 1000.

In certain embodiments, the at least third polymeric arms, for example,as provided in star macromolecules represented by Formulas B or D,covalently attached to the core may be independently represented by t,and may have a value in the range of between 0 to 1000, such as between1 to 1000, between 2 and 1000; between 3 and 1000; between 4 and 1000;between 5 and 1000; between 10 to 1000; between 10 to 500; between 10and 400; between 2 and 500; between 3 and 300; between 4 and 200;between 5 and 150; between 6 and 100; between 7 and 75; between 8 and50; between 9 and 40; between 10 and 30; between 20 and 30; between 20and 40; between 20 and 50; between 25 and 35; between 25 and 45; between25 and 50; between 75 and 125; between 10 and 75; between 12 and 300;between 14 and 200; between 14 and 150; between 15 and 100; between 15and 90; between 15 and 80; between 15 and 70; between 15 and 60; between15 and 50; between 15 and 45; between 15 and 30; between 30 and 45;between 30 and 50; between 50 to 500; between 50 to 400; between 50 to300; between 50 to 200; between 50 and 100; between 100 to 250; between125 to 175; between 150 to 300; between 300 to 800; between 400 to 800;between 500 to 800; between 600 to 800; between 600 to 1000.

Suitable star macromolecules may have more than one arm type, such astwo or more different arm types, where in a molar ratio of the differentarm types may be between 40:1 and 1:40. In certain embodiments, a starmacromolecule may comprise at least two different arm types, forexample, at least a first polymeric arm, for example a hydrophilicpolymeric arm or a polymeric arm represented by [(P1)_(q1)], and atleast a second polymeric arm, for example a polymeric arm comprising asurfactant-system thickening polymeric segment or a micelle-philicpolymeric segment or a polymeric arm represented by-[(P3)_(q3)—(P2)_(q2)], such as in star macromolecules represented byFormulas A or C, and the molar ratio of the two different arm types maybe in the range of between 40:1 to 1:40; such as between 40:1 to 2:1,between 35:1 to 2:1; between 30:1 to 2:1; between 25:1 to 2:1; between20:1 to 2:1; between 15:1 to 2:1; between 10:1 to 2:1; between 9:1 to2:1; between 8:1 to 2:1; between 7:1 to 2:1; between 7:3 to 2:1; between7:5 to 2:1; between 4:5 to 2:1; between 6:1 to 2:1; between 5:1 to 2:1;between 4:1 to 2:1; between 3:1 to 2:1; between 2:1 to 1:1; between 8:1to 3:1; between 7:1 to 2:1; between 5:1 to 3:1; between 4:1 to 3:1;between 2:1 to 40:1; between 2:1 to 35:1; between 2:1 to 30:1; between2:1 to 25:1; between 2:1 to 20:1; between 2:1 to 15:1; between 2:1 to10:1; between 2:1 to 9:1; between 2:1 to 8:1; between 2:1 to 7:1;between 2:1 to 7:3; between 2:1 to 7:5; between 2:1 to 4:5; between 2:1to 6:1; between 2:1 to 5:1; between 2:1 to 4:1; between 2:1 to 3:1;between 1:1 to 2:1; between 3:1 to 8:1; between 2:1 to 7:1; between 3:1to 5:1; or between 3:1 to 4:1.

Suitable star macromolecules may have more than one arm type, such asthree or more different arm types, where in a molar ratio of thedifferent arm types may be between 40:1 and 1:40. In certainembodiments, a star macromolecule may comprise at least three differentarm types, for example, at least a first polymeric arm, for example ahydrophilic polymeric arm or a polymeric arm represented by [(P1)_(q1)],at least a second polymeric arm, for example a polymeric arm comprisinga surfactant-system thickening polymeric segment or a micelle-philicpolymeric segment or a polymeric arm represented by-[(P3)_(q3)-(P2)_(q2)], and at least a third polymeric arm, for examplea polymeric arm comprising a hydrophobic polymeric segment or apolymeric arm represented by -[(P5)_(q5)-(P4)_(q4)], such as in starmacromolecules represented by Formulas B or D, and the molar ratio ofthe three different arm types may include (i) a molar ratio of the atleast first polymeric arms to the at least second polymeric arms; (ii) amolar ratio of the at least first polymeric arms to the at least thirdpolymeric arms; and/or (iii) a molar ratio of the at least firstpolymeric arms to the sum of the at least second polymeric arms and theat least third polymeric arms, and each of these molar ratios mayindependently be in the range of between 40:1 and 1:40; such as between40:1 to 2:1, between 35:1 to 2:1; between 30:1 to 2:1; between 25:1 to2:1; between 20:1 to 2:1; between 15:1 to 2:1; between 10:1 to 2:1;between 9:1 to 2:1; between 8:1 to 2:1; between 7:1 to 2:1; between 7:3to 2:1; between 7:5 to 2:1; between 4:5 to 2:1; between 6:1 to 2:1;between 5:1 to 2:1; between 4:1 to 2:1; between 3:1 to 2:1; between 2:1to 1:1; between 8:1 to 3:1; between 7:1 to 2:1; between 5:1 to 3:1;between 4:1 to 3:1; between 2:1 to 40:1; between 2:1 to 35:1; between2:1 to 30:1; between 2:1 to 25:1; between 2:1 to 20:1; between 2:1 to15:1; between 2:1 to 10:1; between 2:1 to 9:1; between 2:1 to 8:1;between 2:1 to 7:1; between 2:1 to 7:3; between 2:1 to 7:5; between 2:1to 4:5; between 2:1 to 6:1; between 2:1 to 5:1; between 2:1 to 4:1;between 2:1 to 3:1; between 1:1 to 2:1; between 3:1 to 8:1; between 2:1to 7:1; between 3:1 to 5:1; or between 3:1 to 4:1.

Suitable star macromolecules, such as those represented by Formulas A,B, C, or D, may have one or more different types of surfactant-systemthickening polymeric arms covalently attached to the core. In certainembodiments, suitable star macromolecules may have 2 or more differenttypes of surfactant-system thickening polymeric arms covalently attachedto the core, such as in the range of between 1 to 500; between 2 to 450;between 2 to 300; between 2 to 200; between 2 to 100; between 2 to 50;between 1 to 100; between 1 to 20; between 1 to 75; between 10 to 400;between 15 to 200; between 100 to 500; between 250 to 500; between 300to 500; between 40 to 80; between 125 to 325; between 100 to 200; orbetween 15 to 150 different types of surfactant-system thickeningpolymeric arms covalently attached to the core; each surfactant-systemthickening polymeric arm covalently attached to the core is a differentarm type.

Suitable star macromolecules may include, but is not limited to,comprising at least one polymeric arm having a molecular weight ofgreater than 1,000 g/mol, such as greater than 5,000 g/mol. For example,a star macromolecule may comprise at least one polymeric arm, such as atleast two, at least three, or a plurality of polymeric arms, having amolecular weight of between 1,000 g/mol and 400,000 g/mol, such asbetween 2,000 g/mol and 300,000 g/mol; 5,000 g/mol and 200,000 g/mol;5,000 g/mol and 100,000 g/mol; 5,000 g/mol and 75,000 g/mol; 5,000 g/moland 60,000 g/mol; 5,000 g/mol and 50,000 g/mol; 10,000 g/mol and 100,000g/mol; 10,000 g/mol and 150,000 g/mol; between 10,000 g/mol and 125,000g/mol; between 10,000 g/mol and 100,000 g/mol; between 10,000 g/mol and90,000 g/mol; between 10,000 g/mol and 80,000 g/mol; between 10,000g/mol and 70,000 g/mol; between 50,000 g/mol and 60,000 g/mol; between50,000 g/mol and 70,000 g/mol; between 10,000 g/mol and 40,000 g/mol;between 10,000 g/mol and 30,000 g/mol; between 10,000 g/mol and 20,000g/mol; between 20,000 g/mol and 175,000 g/mol; between 20,000 g/mol and100,000 g/mol; between 20,000 g/mol and 75,000 g/mol; between 20,000g/mol and 50,000 g/mol; between 15,000 g/mol and 45,000 g/mol; orbetween 15,000 g/mol and 30,000 g/mol.

In certain embodiments, suitable star macromolecules may have amolecular weight of greater than 5,000 g/mol, such as greater than25,000 g/mol; greater than 50,000 g/mol; or greater than 100,000 g/mol;for example, between 5,000 g/mol and 10,000,000 g/mol, such as between25,000 g/mol and 7,000,000 g/mol; between 50,000 g/mol and 5,000,000g/mol; 20,000 g/mol and 1,000,000 g/mol; between 50,000 g/mol and1,500,000 g/mol; between 100,000 g/mol and 500,000 g/mol; between100,000 g/mol and 1,000,000 g/mol; between 100,000 g/mol and 2,000,000g/mol; between 100,000 g/mol and 2,500,000 g/mol; between 125,000 g/moland 1,750,000 g/mol; between 150,000 g/mol and 1,750,000 g/mol; between200,000 g/mol and 1,500,000 g/mol; between 225,000 g/mol and 1,250,000g/mol; between 125,000 g/mol and 1,000,000 g/mol; between 125,000 g/moland 900,000 g/mol; between 125,000 g/mol and 800,000 g/mol; between125,000 g/mol and 700,000 g/mol; between 150,000 g/mol and 650,000g/mol; between 200,000 g/mol and 500,000 g/mol; between 200,000 g/moland 600,000 g/mol; between 225,000 g/mol and 650,000 g/mol; between250,000 g/mol and 550,000 g/mol; between 350,000 g/mol and 500,000g/mol; between 300,000 g/mol and 500,000 g/mol; between 350,000 g/moland 750,000 g/mol; 750,000 g/mol and 10,000,000 g/mol; 1,250,000 g/moland 8,000,000 g/mol; 2,500,000 g/mol and 5,000,000 g/mol; 4,000,000g/mol and 6,000,000 g/mol; or 5,000,000 g/mol and 10,000,000 g/mol.

Suitable arms of a star macromolecule may include, but is not limitedto, arms having an HLB value of at least 17 (wherein the HLB iscalculated per the formula set forth in the test procedures). Forexample, a suitable arm of a star macromolecule may have an HLB value ofgreater than 17.25, such as greater than 18.5; at least 19; between 17.5to 20; between 17.5 to 19.5; between 18 to 20; between 18.5 to 20;between 19 to 20; between 19.5 to 20; between 18 to 19.5; between 18.5to 19.75; between 18.2 to 19.2; or between 18.75 to 19.5.

Suitable hydrophobic polymeric segments of a copolymeric arm of a starmacromolecule may include, but is not limited to, hydrophobic polymericsegments having an HLB value of less than 8. For example, a suitablehydrophobic polymeric segment may have an HLB value of less than 7, suchas less than 6; less than 5; less than 4; less than 3; less than 2; orabout 1.

Suitable arms of a star macromolecule may include, but is not limitedto, arms having a polydispersity index (PDI) value of less than 3.0. Forexample, a suitable arm of a star macromolecule may have PDI value ofless than 2.5, such as less than 2.25; less than 2.0; less than 1.7;between 1.0 to 3.0, such as between 1.0 and 2.5; between 1.0 and 2.3;between 1.0 and 2.0; between 1.0 and 1.9; between 1.0 and 1.8; between1.0 and 1.7; between 1.0 and 1.6; between 1.0 and 1.5; between 1.0 and1.4; between 1.0 and 1.3; between 1.0 and 1.2; between 1.0 and 1.1;between 1.05 and 1.75; between 1.1 and 1.7; between 1.15 and 1.65; orbetween 1.15 and 1.55.

Suitable star macromolecules may have a single peak in a GPC curve witha polydispersity index (PDI) above 1.0 and below 3.5. For example, asuitable star macromolecule may have a PDI of less than 3.5, such asless than 3, less than 2.5, less than 2.0, or less than 1.7. Forexample, a suitable star macromolecule may have a PDI of between 1.0 to3.5, such as between 1.0 and 3.25; between 1.0 and 3.0; between 1.0 and2.7; between 1.0 and 2.5; between 1.5 and 2.4; between 1.0 and 1.9;between 1.0 and 1.8; between 1.0 and 1.7; between 1.0 and 1.6; between1.0 and 1.5; between 1.0 and 1.4; between 1.0 and 1.3; between 1.0 and1.2; between 1.0 and 1.1; between 1.05 and 1.75; between 1.1 and 1.7;between 1.15 and 1.65; between 1.15 and 1.55; between 1.7 and 2.3.

Suitable cores of a star macromolecule may be formed by, but is notlimited to, crosslinking of a plurality of arms and a crosslinker. Thecore may be a core a hydrophobic core or a hydrophilic core. Forexample, the core of a star macromolecule may be formed by crosslinkinga plurality of polymeric arms with a crosslinker, such as amultifunctional monomer crosslinker, for example, a hydrophobicdifunctional monomer crosslinker. In certain embodiments, the core maybe formed by crosslinking at least one first polymeric arm and at leastone second polymeric arm with a crosslinker, for example crosslinking aplurality of at least one first polymeric arm and a plurality of atleast one second polymeric arm with a crosslinker, such as a hydrophobicdifunctional monomer crosslinker, for example divinylbenzene, whereinthe molar ratio of the at least first polymeric arm to the at leastsecond polymeric arm may be in the range of between 40:1 to 1:40. Forexample, the core of a star macromolecules may be formed by crosslinkingan ATRP-functional terminal group end of the at least first polymericarm with an ATRP-functional terminal group end of the at least secondpolymeric arm.

Suitable star macromolecules may comprise a core having a molecularweight of greater than 3,000 g/mol. For example, a star macromoleculemay comprise a core having a molecular weight of between 3,000 g/mol and100,000 g/mol, such as between 3,000 g/mol and 90,000 g/mol; between3,000 g/mol and 45,000 g/mol; between 3,000 g/mol and 40,000 g/mol;between 3,000 g/mol and 30,000 g/mol; between 3,000 g/mol and 20,000g/mol; between 3,000 g/mol and 15,000 g/mol; between 5,000 g/mol and40,000 g/mol; between 6,000 g/mol and 30,000 g/mol; between 7,000 g/moland 25,000 g/mol; between 8,000 g/mol and 20,000 g/mol; between 5,000g/mol and 15,000 g/mol; between 7,000 g/mol and 12,000 g/mol; between5,000 g/mol and 9,000 g/mol; between 8,000 g/mol and 10,000 g/mol;between 9,000 g/mol and 15,000 g/mol; between 40,000 g/mol and 100,000g/mol; between 50,000 g/mol and 90,000 g/mol; between 60,000 g/mol and85,000 g/mol; between 30,000 g/mol and 50,000 g/mol; or between 75,000g/mol and 100,000 g/mol.

Suitable synthetic methods that may be used for the synthesis of themulti-arm star macromolecules, surfactant-system thickening polymericarms, and/or surfactant-system thickening polymeric segments of theinvention includes, but is not limited to, living ionic polymerization,such as living anionic or living cationic polymerization; free radicalpolymerization, such as living/controlled radical polymerization (CRP),for example, stable free radical polymerization (SFRP), degenerativechain transfer polymerization (DT), or atom transfer radicalpolymerization (ATRP). In certain embodiments, living/controlled radicalpolymerization (CRP) is the preferred process.

Suitable initiators that may be used to form the star macromolecules ofthe present invention, may include, but is not limited to, nitroxideinitiators, such as stable nitroxide initiators, for example,2,2,6,6-Tetramethylpiperidine-1-oxyl, sometimes called TEMPO; transitionmetal complexes, such cobalt containing complexes; ATRP initiators,comprising halides, such as, bromide, chloride, or iodide, andtransition metal sources, such as, copper, iron, ruthenium transitionmetal sources; iodide with RCTP catalysts, such as germanium or tincatalysts; RAFT initiators, such as dithioesters, dithiocarbamates, orxanthates; ITP catalysts, comprising iodides; tellurium compounds (e.g.,TERP); stibine compounds (e.g., SBRP); or bismuth compounds (e.g.,BIRP). For example, in certain embodiments, an initiator may furthercomprise a monomeric residue, a polymeric segment comprising monomericresidues, or a small-molecule, such as diethyl 2-bromo-2-methylmalonate(DEBMM). For example, in certain embodiments, an initiator may comprisean ATRP initiator, wherein the ATRP initiator serves as a terminalfunctional group. For example, in certain embodiments, an initiator maycomprise an ATRP-functional terminal group, comprising an ATRPinitiator, such as halides and transition metal sources.

Suitable radical initiators that may be used to form the starmacromolecules of the present invention, may include, but is not limitedto, azo-containing compounds such as 2,2′-azobis(2-methylpropionitrile)(AIBN); a peroxide, for example, benzoyl peroxide (BPO), lauroylperoxide, or cyclohexanone peroxide; a peroxy acid, for example,peroxyacetic acid or peroxybenzoic acid; tert-butyl peracetate;1,1-bis(tert-butylperoxy)-3,3,5-(dibutyl phthalate)trimethylcyclohexane; 2,2′-azobis(4-methoxy-2.4-dimethyl valeronitrile)(V-70); 2,2′-azobis(2,4-dimethyl valeronitrile) (V-65); dimethyl2,2′-azobis(2-methylpropionate) (V-601);2,2′-azobis(2-methylbutyronitrile) (V-59);1,1′-azobis(cyclohexane-1-carbonitrile) (V-40);2,2′-azobis[N-(2-propenyl)-2-methylpropionamide] (VF-096); orderivatives or combinations thereof. Other suitable radical initiatorsmay include, but are not limited to acetophenone; anisoin;anthraquinone; anthraquinone-2-sulfonic acid sodium salt monohydrate;(benzene) tricarbonylchromium; benzyl; benzoin ethyl ether,4-benzoylbiphenyl;2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone;4,4′-bis(diethylamino)benzophenone; camphorquinone;2-chlorothioxanthen-9-one; (cumene)cyclopentadienyliron(II)hexafluorophosphate; dibenzosuberenone; 2,2-diethoxyacetophenone;4,4′-dihydroxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone;4-(dimethylamino)benzophenone; 4,4′-dimethylbenzil;2,5-dimethylbenzophenone; 3,4-dimethylbenzophenone;4′-ethoxyacetophenone; 2-ethylanthraquinone; ferrocene;3′-hydroxyacetophenone; 4′-hydroxyacetophenone; 3-hydroxybenzophenone;4-hydroxybenzophenone; 1-hydroxycyclohexyl phenyl ketone;2-hydroxy-2-methylpropiophenone; 2-methylbenzophenone;3-methylbenzophenone; methybenzoylformate;2-methyl-4′-(methylthio)-2-morpholinoprpiophenone; phenanthrenequinone;4′-phenoxyacetophenone; thioxanthen-9-one); or derivatives orcombinations thereof.

Suitable star macromolecules may be nano-scale materials with a globularshape, and may be formed by the “arm first” procedure, may have acrosslinked core, may optionally possess multiple segmented arms ofsimilar composition, or combinations thereof. Suitable starmacromolecules may be designed as homo-arm star macromolecules ormikto-arm star macromolecules.

Synthesis of suitable star macromolecules of the present invention maybe accomplished by, for example, “living” polymerization techniques viaone of three strategies: 1) core-first” which may be accomplished bygrowing arms from a multifunctional initiator, 2) “coupling-onto”involving attaching preformed arms onto a multifunctional core, or 3)arm-first” method which involves cross-linking preformed linear armprecursors using, for example, a divinyl compound.

Suitable star macromolecules may be prepared, comprising: preparing aplurality of arms comprising at least two types of arms, wherein afirst-arm-type extends beyond a second-arm-type and said first-arm-typehas a surfactant-system thickening segment on its distal end, wherein atleast a portion of the surfactant-system thickening segment may extendbeyond the length of the second-arm-types either by the size of themonomeric segment or segments (which may be varied by length ofmonomeric residue, degree of polymerization, or both) for which thesurfactant-system thickening segment is attached.

Suitable star macromolecules may be prepared, comprising: preparing aplurality of arms comprising at least three types of arms, wherein afirst-arm-type extends beyond a second-arm-type and said first-arm-typehas a surfactant-system thickening segment (e.g., homopolymeric orcopolymeric) on its distal end, wherein at least a portion of thesurfactant-system thickening segment may extend beyond the length of thesecond-arm-types either by the size of the monomeric segment or segments(which may be varied by length of monomeric residue, degree ofpolymerization, or both) for which the surfactant-system thickeningsegment is attached; and wherein a third-arm-type extends beyond asecond-arm-type and said third-arm-type has a hydrophobic segment (e.g.,homopolymeric or copolymeric) on its distal end, wherein at least aportion of the hydrophobic segment (e.g., homopolymeric or copolymeric)may extend beyond the length of the second-arm-types either by the sizeof the monomeric segment or segments (which may be varied by length ofmonomeric residue, degree of polymerization, or both) for which thehydrophobic segment (e.g., homopolymeric or copolymeric) is attached.

Suitable star macromolecules may be prepared, comprising: preparing aplurality of arms comprising at least two types of arms, wherein thedegree of polymerization of a first-arm-type is greater than the degreeof polymerization of a second-arm-type, and wherein said first-arm-typehas a distal end portion that is surfactant-system thickening. Forexample, suitable star macromolecules may be prepared by first formingor obtaining the surfactant-system thickening portion then forming theremaining portion of the first-arm-type from the end of thesurfactant-system thickening portion and the second-arm-type, in aone-pot synthesis, wherein the polymerization of the second portion ofthe first-arm-type is commenced prior to the initialization of thesecond-arm-type but there is at least some point wherein portions, e.g.,substantial portions, of the first-arm-type and second-arm-type arebeing polymerically extended simultaneously.

Suitable star macromolecules may be prepared, comprising: a plurality ofarms comprising at least three types of arms, wherein the degree ofpolymerization of a first-arm-type and a third-arm-type are greater thanthe degree of polymerization of a second-arm-type, and wherein saidfirst-arm-type and said third-arm-type have a distal end portion that ishydrophobic and surfactant-system thickening, respectively. For example,suitable star macromolecules may be prepared by first forming orobtaining the hydrophobic portion and the surfactant-system thickeningportion then forming the remaining portion of the first-arm-type fromthe end of the hydrophobic, the third-arm-type from the end of thesurfactant-system thickening portion, and the second-arm-type, in aone-pot synthesis, wherein the polymerization of the second portion ofthe first-arm-type and the second portion of the third-arm-type arecommenced prior to the initialization of the second-arm-type but thereis at least some point wherein portions, e.g., substantial portions, ofthe first-arm-type, third-arm-type, and second-arm-type are beingpolymerically extended simultaneously.

Suitable star macromolecules may be prepared using a one-pot method,comprising: preparing one or more of a first arm, and after achieving ahigh conversion of the monomer, initiate preparing one or more of asecond arm in the same pot, while optionally, extending the prepared oneor more first arms, followed by crosslinking the prepared one or morefirst arms and the prepared one or more second arms, washing theresulting product and isolating the final star macromolecule. The onepot method may further comprise the preparation of more than two arms inthe one pot prior to the crosslinking step, such as preparing one ormore of at least 3 arm types, at least 4, at least 5, at least 10, atleast 15, at least 20 arm types in the one pot, for example, between2-30, such as between 2-25, between 2-20, between 2-15, between 2-10,between 2-8, between 2-6, between 3-30, between 3-25, between 3-20,between 3-15, between 3-10, between 3-7, between 3-5, between 4-15,between 5-20, between 5-10, between 10-20, or between 20-30, arm typesin the one pot.

In certain embodiments, the one pot method may comprise preparing one ormore of a first arm of a star macromolecule by feeding a first amount ofa radical initiator in a controlled manner to a reaction vesselcontaining a first group of monomers at a pre-determined temperature,followed by polymerizing the first group of monomers to greater than 10%monomer conversion, for example polymerizing the first group of monomersto greater than 15% monomer conversion, such as greater than 20%;greater than 25%; greater than 30%; greater than 35%; greater than 40%;greater than 45%; or greater than 50% monomer conversion; for examplebetween 10 and 97% monomer conversion, such as between 15 and 97%;between 15 and 95%; between 15 and 90%; between 15 and 85%; between 15and 80%; between 15 and 75%; between 15 and 70%; between 15 and 65%;between 15 and 50%; between 15 and 45%; between 15 and 40%; between 15and 35%; between 25 and 97%; between 25 and 75%; between 35 and 80%; orbetween 50 and 97% monomer conversion. Upon achieving greater than 10%monomer conversion in preparing the one or more first arms, one or moreof a second arm of the star macromolecule, and optionally, extending theprepared one or more first arms, may begin, comprising: adding a secondarm initiator to the reaction vessel, adding a second group of monomersto the reaction vessel, and feeding (at a pre-determined temperature) asecond amount of the radical initiator in a controlled manner to thereaction vessel containing the second arm initiator, the second group ofmonomers, and optionally the prepared one or more first arms, followedby polymerizing the second group of monomers to greater than 10% monomerconversion. For example polymerizing the second group of monomers togreater than 15% monomer conversion, such as greater than 20%; greaterthan 25%; greater than 30%; greater than 35%; greater than 40%; greaterthan 45%; or greater than 50% monomer conversion; for example between 10and 97% monomer conversion, such as between 15 and 97%; between 15 and95%; between 15 and 90%; between 15 and 85%; between 15 and 80%; between15 and 75%; between 15 and 70%; between 15 and 65%; between 15 and 50%;between 15 and 45%; between 15 and 40%; between 15 and 35%; between 25and 97%; between 25 and 75%; between 35 and 80%; or between 50 and 97%monomer conversion. Upon achieving greater than 10% monomer conversionin preparing the one or more second arms, and optionally, extending theprepared one or more first arms, further arm types may be initiated inthe one pot, such as a third arm type, or more than 3 arm types,following similar steps in preparing the first and second arm types, orthe total group of arms may be crosslinked to form the eventual starmacromolecule. If the total range of arm types has been achieved, thenthe monomer conversion may be driven to a certain amount, for example,at least 70%, prior to beginning the crosslinking. For example afterinitiating the preparation of the last arm type to be incorporated intothe desired star macromolecule, and prior to beginning the crosslinkingstep, the polymerization of the monomers in the reaction vessel may bedriven to greater than 70%, such as greater than 75%; greater than 80%;greater than 85%; greater than 90%; greater than 95%; or greater than97% monomer conversion, prior to beginning the crosslinking step; forexample between 70 and 97% monomer conversion, such as between 75 and97%; between 80 and 97%; between 85 and 95%; between 70 and 90%; between85 and 97%; or between 90 and 97% monomer conversion prior to beginningthe crosslinking step. The crosslinking of the total group of arms typesprepared in the one method may comprise adding the crosslinking agent,and continuing the polymerization in the one pot. The resulting productmay then be washed and isolated.

In certain embodiments, the one pot method of preparing starmacromolecules may reduce the total preparation time of the starmacromolecule by at least 50%, relative to multi-pot preparations, forexample, by at least 55%, such as at least 60%; at least 65%; at least70%; at least 75%; at least 80%; at least 85%; at least 90%; or at least95%, relative to multi-pot preparations. In certain embodiments, the onepot method of preparing star macromolecules may be exclusive ofintermediate purification steps, or may one require one intermediatewashing step or one washing step after crosslinking.

In certain embodiments, suitable star macromolecules may be preparedwith composition and molecular weight of each segment predetermined toperform as rheology modifiers in aqueous based solutions. For example,the first formed segmented linear polymer chains may be chain extendedwith a crosslinker forming a crosslinked core.

In certain embodiments, an industrially scalable process for thepreparation of star macromolecules may be provided, wherein thepolymeric arms may comprise segments selected to induce self assemblyand wherein the self assemblable star macromolecules may be suitable foruse as rheology control agents in waterborne and solvent-borne coatings,adhesives, and fracturing fluid compositions.

In certain embodiments, polymeric segments of the polymeric arms in thestar macromolecule may be selected to induce self assembly when the starmacromolecule is dispersed in a liquid. The self assembling starmacromolecules may be suitable for use as thickening agents or rheologymodifiers in cosmetic and personal care compositions at lowconcentrations of the solid in the thickened solution, for example,present at a concentration of less than 5 wt. %, such as less than 1 wt.%, or present at a concentration of at least 0.0001 wt. %, such as atleast 0.001 wt. %, at least 0.01 wt. %, at least 0.02 wt. %, or at least0.05 wt. %. The dispersion medium may comprise aqueous based systems oroil based systems.

In certain embodiments, suitable surfactants may be modified orincorporated into the star macromolecules of the present invention, forexample, modified to become a polymerizable monomer, such as asurfactant-system thickening monomer or a micelle-philic monomer. Incertain embodiments, suitable surfactants may be modified to attach orbind, such as covalently bond to, a reactive site on a polymeric arm ofa star macromolecule, to become a pendant moiety of the polymeric arm,such as a surfactant-system thickening pendant moiety or amicelle-philic pendant moiety. In certain embodiments, suitablesurfactants may be included in the system, such as an aqueous system,into which a star macromolecule of the present invention may beintroduced to influence the rheological properties of the system, forexample, thicken or increase the viscosity of the system, provide shearthinning properties, provide temperature stability, provide pHefficiency within a pH range, or combinations thereof.

In certain embodiments, suitable nonionic surfactants may include, butare not limited to: fatty alcohol, for example, cetyl alcohol, stearylalcohol, cetostearyl alcohol, oleyl alcohol, or a residue of a fattyalcohol; surfactants having one or more poly(oxyethylene) chains astheir hydrophilic part; an amine oxide, for example,dodecyldimethylamine oxide; an ethoxylated or propoxylated alkyl phenol,for example, an ethoxylated or propoxylated C₄₋₄₀ alkyl phenol, such as,an ethoxylated or propoxylated octyl phenol, an ethoxylated orpropoxylated nonyl phenol, an ethoxylated or propoxylated decyl phenol,or an ethoxylated or propoxylated dodecyl phenol; an ethoxylated orpropoxylated fatty alcohol, for example, an ethoxylated or propoxylatedlinear or branched C₄₋₄₀ alkyl alcohol, such as ethoxylated orpropoxylated decyl alcohol, ethoxylated or propoxylated isodecylalcohol, ethoxylated or propoxylated lauryl alcohol, ethoxylated orpropoxylated tridecyl alcohol, ethoxylated or propoxylated isotridecylalcohol, ethoxylated or propoxylated cetyl alcohol, ethoxylated orpropoxylated stearyl alcohol, ethoxylated or propoxylated cetostearylalcohol, ethoxylated or propoxylated arachidyl alcohol, ethoxylated orpropoxylated behenyl alcohol, ethoxylated or propoxylated lignocerylalcohol, or ethoxylated or propoxylated ceryl alcohol; a polyethyleneglycol (of all molecular weights and reactions); a polypropylene glycol(of all molecular weights and reactions); saturated or unsaturated fattyacid amides, for example, capra/caprylamide diethanolamide, coconutfatty acid monoethanolamide (cocamide MEA), or coconut fatty aciddiethanolamide (cocamide DEA); glucoside C₆₋₄₀ alkyl ethers, forexample, octyl glucoside, N-octyl beta-D-thioglucopyranoside, decylglucoside, lauryl glucoside, stearyl glucoside, or behenyl glucoside;Cetomacrogol 1000; glycerol alkyl esters, for example glyceryl laurate(monolaurin); polyglycerol alkyl esters; polyglycerol polyricinoleate;polyoxyethylene glycol alkyl ethers (BRIJ®), for example, C₈₋₄₀alkyl-(O—C₂H₄)₁₋₂₅ OH, such as pentaethylene glycol monododecyl ether,octaethylene glycol monododecyl ether, or Isoceteth-20; polyoxypropyleneglycol alkyl ethers, for example, C₈₋₄₀ alkyl-(O—C₃H₆)₁₋₂₅ OH;polyoxyethylene glycol alkylphenol ethers, for example C₆₋₄₀alkyl-(C₆H₄)—(O—C₃H₆)₁₋₂₅ OH, such as polyoxyethylene glycol octylphenolethers: C₈ alkyl-(C₆H₄)—(O—C₃H₆)₁₋₂₅ OH, such asoctylphenoxypolyethoxyethanol (nonidet P-40), or nonylphenoxypolyethoxylethanol, such as NP-40, polyoxyethylene glycolsorbitan alkyl esters (Polysorbate), for example, Polysorbate 20 orPolysorbate 80; sorbitan alkyl esters (Spans); sorbitan fatty alkylesters, for example, sorbitan monostearate, or sorbitan tristearate;block copolymers of polyethylene glycol and polypropylene glycol(Poloxamers), for example, Poloxamer 407; polyethoxylated tallow amine(POEA) salt; nonoxynols, for example, Nonoxynol-9; Triton X-100; orTween 80.

In certain embodiments, suitable anionic surfactants, may include, butare not limited to compounds having carboxylate, sulfate, sulfonate,and/or phosphate polar groups, in combination with counterions, forexample, alkali metal cations, such as sodium or potassium, alkalineearth metal cations, such as calcium or magnesium, or ammonium cations,such as tetraalkyl ammonium cations. Suitable anionic surfactants maygenerally include salts (including, for example, sodium, potassium,ammonium, and substituted ammonium salts such as mono-, di-, andtriethanolamine salts) of the anionic sulfate, sulfonate, carboxylateand sarcosinate surfactants. In certain embodiments, suitable anionicsurfactants may include isethionates, such as the acyl isethionates,N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates,sulfoacetates, and sulfosuccinates, monoesters of sulfosuccinate, suchas saturated and unsaturated C₁₂-C₁₈ monoesters of sulfosuccinate,diesters of sulfosuccinate, such as saturated and unsaturated C₆-C₁₄diesters of sulfosuccinate, and N-acyl sarcosinates. Resin acids andhydrogenated resin acids may also be suitable as anionic surfactants,such as rosin, hydrogenated rosin, and resin acids and hydrogenatedresin acids present in or derived from tallow oil.

In certain embodiments, suitable anionic surfactants may be selectedfrom alkyl sulfates, such as sodium lauryl sulfate, alkyl ethersulfates, such as sodium lauryl ether sulfate (SLES), alkyl estersulfonates, alpha olefin sulfonates, linear alkyl benzene sulfonates,branched alkyl benzene sulfonates, linear dodecylbenzene sulfonates,branched dodecylbenzene sulfonates, alkyl benzene sulfonic acids, suchas dodecylbenzene sulfonic acid, sulfosuccinates, such as or sodiumdioctyl sulfosuccinate, sulfated alcohols, ethoxylated sulfatedalcohols, alcohol sulfonates, ethoxylated and propoxylated alcoholsulfonates, alcohol ether sulfates, ethoxylated alcohol ether sulfates,propoxylated alcohol sulfonates, sulfated nonyl phenols, ethoxylated andpropoxylated sulfated nonyl phenols, sulfated octyl phenols, ethoxylatedand propoxylated sulfated octyl phenols, sulfated dodecyl phenols,ethoxylated and propoxylated sulfated dodecyl phenols. In certainembodiments, suitable anionic surfactants may also include dicarboxylicacids, phosphate esters, sodium xylene sulfonate, and sodium dodecyldiphenyl ether disulfonate. In certain embodiments, suitable anionicsulfate surfactants may include, for example, linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleylglycerol sulfates, alkyl phenol ethoxylate sulfates, alkyl phenolethylene oxide ether sulfates, C₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides,such as sulfates of alkylpolyglucoside. In certain embodiments, suitableanionic surfactants may also include anionic polymers, for example, ahydratable polysaccharide, such as hydroxypropyl guar, carboxymethylguar, and carboxymethyl hydroxylpropyl guar.

In certain embodiments, suitable cationic surfactants may have a chargecarried on a nitrogen atom, such as with amine and quaternary ammoniumsurfactants. Generally, the quaternary ammonium compounds retain thischarge over the whole pH range, whereas amine-based compounds may onlyfunction as surfactants in the protonated state. Suitable cationicsurfactants may include, but are not limited to octenidinedihydrochloride; permanently charged quaternary ammonium cationcompounds, such as alkyltrimethyl-ammonium salts: cetyltrimethylammonium bromide (CTAB), i.e., hexadecyl trimethyl ammoniumbromide, cetyl trimethylammonium chloride (CTAC), Cetylpyridiniumchloride (CPC), Benzalkonium chloride (BAC), Benzethonium chloride(BZT), 5-Bromo-5-nitro-1,3-dioxane, Dimethyldioctadecylammoniumchloride, Cetrimonium bromide, and Dioctadecyldimethylammonium bromide(DODAB).

In certain embodiments, suitable amphoteric surfactants (zwitterionicsurfactants) possess polar head groups, which on ionization, may impartboth positive and negative charges. For example, the positive charge maybe carried by an ammonium group, such as a primary, secondary, ortertiary amines or quaternary ammonium cations, and the negative chargemay be a carboxylate, a sulfonates, such as in CHAPS(3-[(3-Cholamidopropyl)-dimethylammonio]-1-propanesulfonate). Othersuitable anionic groups may be sultaines, such as cocamidopropylhydroxysultaine. In certain embodiments, suitable amphoteric surfactantsmay include, but are not limited to, N-alkyl derivatives of simple aminoacids, such as glycine (NH₂CH₂COOH), aminopropionic acid (NH₂CH₂CH₂COOH)and alkyl betaines, N-coco 3-aminopropionic acid/sodium salt, N-tallow3-iminodipropionate, disodium salt, N-carboxymethyl N dimethyl N-9octadecenyl ammonium hydroxide, N-cocoamidethyl N hydroxyethylglycine,sodium salt, betaines, such as cocamidopropyl betaine,capryl/capramidopropil betaine, and coco betaine; phosphates, andlecithin.

In certain embodiments, suitable star macromolecules, or a method ofmaking or using the same, may form an aqueous gel (e.g., a clear,homogeneous aqueous gel) when prepared according to the SamplePreparation Procedure at a concentration of at least 0.0001 wt. % at apH of about 7.5 at STP, such as at least 0.001 wt. %; at least 0.01 wt.%, at least 0.02 wt. %, or at least 0.05 wt. % at a pH of about 7.5 atSTP. For example, an aqueous gel of a suitable star macromolecule mayform when prepared according to the Sample Preparation Procedure at aconcentration of between 0.05 wt. % to 3 wt. %, such as between 0.1 wt.% to 2.5 wt. %; between 0.1 wt. % to 2 wt. %; between 0.2 wt. % to 2.0wt. %; between 0.2 wt. % to 1.5 wt. %; between 0.2 wt. % to 1.0 wt. %;between 0.2 wt. % to 2.5 wt. %; between 0.3 wt. % to 2.5 wt. %; between0.4 wt. % to 2.0 wt. %; between 0.5 wt. % to 2.0 wt. %; between 0.6 wt.% to 2.0 wt. %; between 0.7 wt. % to 1.5 wt. %; between 0.8 wt. % to 1.2wt. %; between 0.9 wt. % to 1.1 wt. %; between 0.5 wt. % to 2.5 wt. %;between 0.75 wt. % to 1.5 wt. %; or between 0.8 wt. % to 1.6 wt. %.

In certain embodiments, suitable star macromolecules, or a method ofmaking or using the same, may form an aqueous gel (e.g., a clear,homogeneous aqueous gel) at a concentration of 0.4 wt. % and has adynamic viscosity of at least 5,000 cP at a shear rate of 2.2 s⁻¹ at 25°C., according to the Thickening and Shear Thinning in Water Test, forexample, has a dynamic viscosity of at least 5,500 cP, such as at least6,000 cP; at least 7,000 cP; at least 8,500 cP; at least 10,000 cP; atleast 12,500 cP; at least 15,000 cP; at least 20,000 cP; or at least20,000 cP, according to the Thickening and Shear Thinning in Water Test.In certain embodiments, aqueous gels formed from suitable starmacromolecules may further have a shear thinning value of at least 60%,for example, at least 70%; at least 75%; at least 80%; at least 85%; orat least 90%, according to the Thickening and Shear Thinning in WaterTest.

In certain embodiments, suitable star macromolecules, or a method ofmaking or using the same, may form an aqueous gel (e.g., a clear,homogeneous aqueous gel) at a concentration of 2.0 wt. % and has adynamic viscosity of at least 500 cP at a shear rate of 2.2 s⁻¹ at 25°C., according to the SLES Surfactant Compatibility Test, for example,has a dynamic viscosity of at least 600 cP, such as at least 800 cP; atleast 1,000 cP; at least 1,500 cP; at least 2,000 cP; at least 2,500 cP;at least 3,000 cP; at least 4,000 cP; at least 5,000 cP; at least 8,000cP; at least 10,000 cP; according to the SLES Surfactant CompatibilityTest. In certain embodiments, aqueous gels formed from suitable starmacromolecules may further have a shear thinning value of at least 60%,for example, at least 70%; at least 75%; at least 80%; at least 85%; orat least 90%, according to the SLES Surfactant Compatibility Test.

In certain embodiments, suitable star macromolecules, or a method ofmaking or using the same, may form an aqueous gel (e.g., a clear,homogeneous aqueous gel) at a concentration of 2.0 wt. % and has adynamic viscosity of at least 5,000 cP at a shear rate of 2.2 s⁻¹ at 25°C., according to the Hybrid SLES-CH Surfactant Compatibility Test, forexample, has a dynamic viscosity of at least 6,000 cP, such as at least7,000 cP; at least 8,500 cP; at least 10,000 cP; at least 12,500 cP; atleast 15,000 cP; at least 18,000 cP; at least 20,000 cP; at least 25,000cP; at least 30,000 cP; at least 35,000 cP; at least 40,000 cP; at least45,000 cP; or at least 50,000 cP, according to the Hybrid SLES-CHSurfactant Compatibility Test. In certain embodiments, aqueous gelsformed from suitable star macromolecules may further have a shearthinning value of at least 35%, for example, at least 40%; at least 45%;at least 50%; at least 60%; at least 70%; at least 75%; at least 80%; atleast 85%; or at least 90%, according to the Hybrid SLES-CH SurfactantCompatibility Test.

In certain embodiments, suitable star macromolecules, or a method ofmaking or using the same, may form an aqueous gel (e.g., a clear,homogeneous aqueous gel) at a concentration of 1.5 wt. % and has adynamic viscosity of at least 1,500 cP at a shear rate of 2.2 s⁻¹ at 25°C., according to the Hybrid CB-SLES Surfactant Compatibility Test, forexample, has a dynamic viscosity of at least 2,000 cP, such as at least2,500 cP; at least 3,000 cP; at least 4,000 cP; at least 5,000 cP; atleast 7,000 cP; at least 10,000 cP; at least 15,000 cP; at least 18,000cP; or at least 20,000 cP, according to the Hybrid CB-SLES SurfactantCompatibility Test. In certain embodiments, aqueous gels formed fromsuitable star macromolecules may further have a shear thinning value ofat least 15%, for example, at least 20%; at least 25%; at least 30%; atleast 40%; at least 50%; at least 60%; at least 70%; at least 75%; atleast 80%; at least 85%; or at least 90%, according to the HybridCB-SLES Surfactant Compatibility Test.

In certain embodiments, suitable star macromolecules, or a method ofmaking or using the same, may form an aqueous gel (e.g., a clear,homogeneous aqueous gel) at a concentration of 1.5 wt. % and has adynamic viscosity of at least 1,500 cP at a shear rate of 0.22 s⁻¹ at25° C., according to the Hybrid CB-SLES Surfactant with NaClCompatibility Test, for example, has a dynamic viscosity of at least1,500 cP, such as at least 2,000 cP; at least 2,500 cP; at least 3,000cP; at least 4,000 cP; at least 5,000 cP; at least 7,000 cP; at least10,000 cP; at least 15,000 cP; at least 20,000 cP; at least 30,000 cP;at least 40,000 cP; at least 50,000 cP; or at least 60,000 cP, accordingto the Hybrid CB-SLES Surfactant with NaCl Compatibility Test. Incertain embodiments, aqueous gels formed from suitable starmacromolecules may further have a shear thinning value of at least 15%,for example, at least 20%; at least 25%; at least 30%; at least 40%; atleast 50%; at least 60%; at least 70%; at least 75%; at least 80%; atleast 85%; or at least 90%, according to the Hybrid CB-SLES Surfactantwith NaCl Compatibility Test. In certain embodiments, the aqueous gelsformed from suitable star macromolecules may have 10 wt. % NaCl, and theresulting gel may have a dynamic viscosity of at least 2.500 cP at ashear rate of 0.22 s⁻¹ at 25° C., according to the Hybrid CB-SLESSurfactant with NaCl Compatibility Test, for example, have a dynamicviscosity of at least 5,000 cP, such as at least 7,000 cP; at least10,000 cP; at least 15,000 cP; at least 20,000 cP; at least 30,000 cP;at least 40,000 cP; at least 50,000 cP; at least 60,000 cP; at least70,000 cP; at least 80,000 cP; at least 90,000 cP; or at least 100,000cP, according to the Hybrid CB-SLES Surfactant with NaCl CompatibilityTest.

In certain embodiments, suitable star macromolecules, or a method ofmaking or using the same, may form an aqueous gel (e.g., a clear,homogeneous aqueous gel) at a concentration of 2.0 wt. % and has adynamic viscosity of at least 15,000 cP at a shear rate of 2.2 s⁻¹ at25° C., according to the Ritabate 20 Surfactant Compatibility Test, forexample, has a dynamic viscosity of at least 18,000 cP, such as at least20.00 cP; at least 25,000 cP; at least 30,000 cP; or at least 35,000 cP,according to the Ritabate 20 Surfactant Compatibility Test.

In certain embodiments, suitable star macromolecules, or a method ofmaking or using the same, may form an aqueous gel (e.g., a clear,homogeneous aqueous gel) at a concentration of 2.0 wt. % and has adynamic viscosity of at least 1,500 cP at a shear rate of 2.2 s⁻¹ at 25°C., according to the APG Surfactant Compatibility Test, for example, hasa dynamic viscosity of at least 2,000 cP, such as at least 2,500 cP; atleast 2,750 cP; at least 3,000 cP; or at least 3,500 cP, according tothe APG Surfactant Compatibility Test.

In certain embodiments, suitable star macromolecules, or a method ofmaking or using the same, may form an aqueous gel (e.g., a clear,homogeneous aqueous gel) at a concentration of 0.4 wt. %, when preparedaccording to the Sample Preparation Procedure, and has a dynamicviscosity of at least 100,000 cP at a shear rate of 0.22 s⁻¹ at 25° C.,and has a Dynamic Viscosity at 80° C. that is at least 50% relative tothe viscosity of the gel at 25° C., according to the TemperatureStability Test, for example, a dynamic viscosity at 80° C. that is atleast 60% relative to the viscosity of the gel at 25° C., such as atleast 70%; at least 75%; at least 80%; at least 85%; or at least 90%,relative to the viscosity of the gel at 25° C., according to theTemperature Stability Test; or is greater than the viscosity of the gelat 25° C., according to the Temperature Stability Test.

In certain embodiments, suitable star macromolecules, or a method ofmaking or using the same, may form an aqueous gel (e.g., a clear,homogeneous aqueous gel) at a concentration of 1.5 wt. % and has adynamic viscosity of at least 7,000 cP at a shear rate of 0.22 s⁻¹ at25° C., according to the pH Efficiency Range in Hybrid CB/SLESSurfactant Test, for example, has a dynamic viscosity of at least 8,000cP, such as at least 10.00 cP; at least 15,000 cP; at least 20,000 cP;at least 25,000 cP; at least 30,000 cP; at least 50,000 cP; at least75,000 cP; at least 80,000 cP; or at least 90,000 cP, according to thepH Efficiency Range in Hybrid CB/SLES Surfactant Test.

In certain embodiments, suitable star macromolecules, or a method ofmaking or using the same, may form an aqueous gel (e.g., a clear,homogeneous aqueous gel) at a concentration of 0.4 wt. % and has adynamic viscosity of at least 4,000 cP at an adjusted pH in the range ofbetween 5 to 12 at a shear rate of 0.22 s⁻¹ at 25° C., according to thepH Efficiency Range Test, for example, has a dynamic viscosity of atleast 8,000 cP, such as at least 10.00 cP; at least 15,000 cP; at least20,000 cP; at least 25,000 cP; at least 30,000 cP; at least 50,000 cP;at least 75,000 cP; at least 80,000 cP; at least 90,000 cP; or at least95,000 cP, according to the pH Efficiency Range Test. In certainembodiments, suitable star macromolecules, or a method of making orusing the same, may form an aqueous gel (e.g., a clear, homogeneousaqueous gel) at a concentration of 0.4 wt. % and has a dynamic viscosityof at least 40,000 cP at an adjusted pH in the range of between 6 to 10at a shear rate of 0.22 s⁻¹ at 25° C., according to the pH EfficiencyRange Test, for example, has a dynamic viscosity of at least 45,000 cP,such as at least 50,000 cP; at least 75,000 cP; at least 80,000 cP; atleast 90,000 cP; or at least 100,000 cP, according to the pH EfficiencyRange Test. In certain embodiments, suitable star macromolecules, or amethod of making or using the same, may form an aqueous gel (e.g., aclear, homogeneous aqueous gel) at a concentration of 0.4 wt. % and hasa dynamic viscosity of at least 80,000 cP at an adjusted pH in the rangeof between 8 to 10 at a shear rate of 0.22 s⁻¹ at 25° C., according tothe pH Efficiency Range Test, for example, has a dynamic viscosity of atleast 85,000 cP, such as at least 90,000 cP; or at least 100,000 cP,according to the pH Efficiency Range Test. In certain embodiments,suitable star macromolecules, or a method of making or using the same,may form an aqueous gel (e.g., a clear, homogeneous aqueous gel) at aconcentration of 0.4 wt. % and has a dynamic viscosity of at least60,000 cP at an adjusted pH in the range of between 5.5 to 6.5 at ashear rate of 0.22 s⁻¹ at 25° C., according to the pH Efficiency RangeTest, for example, has a dynamic viscosity of at least 65,000 cP, suchas at least 70,000 cP; or at least 75,000 cP, according to the pHEfficiency Range Test.

In certain embodiments, suitable star macromolecules may providesurfactant compatibility, surfactant-system thickening, an increase inviscosity of a surfactant-containing system, such as an increase inviscosity of a surfactant-containing aqueous system, use as thickeningagents, use as rheology modifiers, use in hydraulic fracturing fluids,use in oil and gas applications, use in mining applications, use incosmetic and personal care applications, use in home care applications,use in paint and printing, use in adhesive applications, use inelectronic applications, use in medical and pharmaceutical applications,use in paper applications, or use in agricultural applications.

In certain embodiments, suitable star macromolecules may provide, or maybe used to provide, a certain level of control over viscosity, anincrease in viscosity of a system, and consistency factors in manyaqueous and oil based systems, including, for example, hydraulicfracturing fluid additives, gelling agents, gels, proppant stabilizers,breakers, friction reducers, and thickening agents.

In an embodiment, the polymer compositions having star macromolecules ofthe present invention, the star macromolecule, emulsifier, gel,emulsifier-free emulsion, emulsion and/or thickening agent, includingthose formed by a one-pot process, living ionic polymerization, such asliving anionic or living cationic polymerization; free radicalpolymerization, such as living/controlled radical polymerization (CRP),for example, stable free radical polymerization (SFRP), degenerativechain transfer polymerization (DT), or atom transfer radicalpolymerization (ATRP), and/or combinations of one or more of theseprocesses, may be used to provide a certain level of control overviscosity and consistency factors in many aqueous and oil based systemsincluding, for example, fracking fluid additives, gelling agents, gels,proppant stabilizers, breakers, friction reducers, thickening agents.

In certain embodiments, the star macromolecule may be suitable in oiland gas applications, including but not limited to, as rheologymodifiers for fracturing fluids/drilling well fluids, gelling agents,gels, dispersants, proppant stabilizers and carriers, breakers, frictionreducers, lubricants, scale-buildup inhibitors, heat transfer fluids,thickening agents, additives to improve oil extraction from oil sands,emulsion breakers for oil-sand-water emulsions, additives to improvedewatering of oil sands, gasoline additives, gasoline stabilizers,coiled tubing clean out fluids, drilling fluids, completion fluids,stimulation fluids, production fluids, hydraulic fracturing fluids,injection fluids, flooding fluids, flow assurance fluids, hydrateinhibitors, asphaltene inhibitors, asphaltenes inhibitors, scaleinhibitors, paraffin inhibitors, friction reducers, corrosioninhibitors, H2S scavengers, de-emulsifiers, foam controlling agents,de-foaming agents, lubricants, scale removers, asphaltene removers, dragreducers, pour point depressants, cold flow improvers, traceablechemicals, foaming agents, viscoelasctic surfactants, and/orviscoelastic surfactant fluid additives.

In certain embodiments, the star macromolecule may be suitable in miningapplications, including but not limited to, concentration of grindingcircuit; leach; concentrate tailings; Counter Current Decantation (CCD);paste backfill; clarification; dust suppressants; flocculating agents;carbon powder recycling; coal, diamond, gold and precious metalextraction and processing; lubricants and drag reduction agents forpipeline slurry transport; flocculants; scale inhibitors; frothers;defoamers; dewatering agents; crystal growth modifiers; filtration aids;dust control agent; dispersant; depressant; thickener; clarifier,solvent extraction reagent; antiscalant aid; and/or smoothing aid.

In certain embodiments, the star macromolecule may be suitable incosmetic and personal care applications, including but not limited to,cosmetic creams, lotions, gels, sprayable lotion, sprayable cream,sprayable gel, hair styling agents, hair styling sprays and mousses,mouse, hair conditioners, shampoos, bath and shower preparations, showergel, hair gel, hair care product, ointments, deodorants andantiperspirants, anti-persperant ingredient, deodorant ingredient,mascara, blush, lip stick, eye liner, perfumes, powders, serums, skinsensoric, skin cleansers, skin conditioners, emollient, skin emollients,skin moisturizers, moisturizer, skin wipes, sensory modifier, skin careproduct, make-up remover, eye cream, leave-on product, wash off product,products for care of the teeth and the mouth, whitening products,mouthwash, products for external intimate hygiene, sunscreens, productsfor tanning without sun, shaving preparations, shaving cream,depilatories, products removing make-up, products for external intimatehygiene, spermicides, condom lubricant, personal hygiene lubricant,solids, fabric softeners, cleansing product, cleansing spray,emulsifier, wetting agent, foamer, soap, soaps, liquid soap, handsanitizer, hand gel, conditioner, humectant, foam stabilizer, softener,clarifier, film former, delivery system, oil deliver system, activedeliver system, rheology modifier, thickening agent, viscosifier, andlubricant.

In certain embodiments, the star macromolecule may be suitable in homecare applications, including but not limited to, cleaners for windowsand glass, and other household surfaces; cleaners for toilet areas; hardsurface cleaners; household cleaners; industrial cleaners; windowcleaners; floor cleaners; shower cleaners; drain cleaners; ovencleaners; tub, tile and sink cleaners; bleach; bleach containingcleaners; degreasers; enzyme production; liquid and gelled soaps;polishes and waxes; car wax; floor wax; polishes; polish; detergents;liquid and powdered detergents, including detergents for laundry and indish washing; laundry detergents; laundry softeners; hard water mineralremovers; metal cleaner and polishes; carpet and rug cleaners; dustingproducts; upholstery cleaners; and floor care products.

In certain embodiments, the star macromolecule may be suitable in paintand printing applications, including but not limited to, inkjet printerink and other inks, 3-D printing fluid, 3-D printing ink, pigments,wetting surfactants, binders, flocculants, dispersants, levelingcompounds, antifoam, aerators, surface tension modifiers, film formers,plasticizers, pore formers, water repellents, corrosion inhibitors,bittering agents to deter rodents.

In certain embodiments, the star macromolecule may be suitable inadhesive applications, including but not limited to, associativecomplexes, billboard adhesives, carpet backsizing compounds, hot meltadhesives, labeling adhesives, latex adhesives, leather processingadhesives, plywood laminating adhesives, paper adhesives, 3-D printingadhesive, 3-D printing binder, wallpaper pastes, wood glue.

In certain embodiments, the star macromolecule may be suitable inelectronic applications, including but not limited to, antistatic filmand packaging, conductive inks, rheology control agents used for copperfoil production, multilayer ceramic chip capacitors, photoresists,plasma display screens, lubricants for wire, cable, and optical fibers,gel lacquers for coil coating.

In certain embodiments, the star macromolecule may be suitable inmedical and pharmaceutical applications, including but not limited to,but not limited to, medical device lubrication, antibacterial coatings,pharmaceutical excipients such as binders, creams, ointments, liniments,pastes, diluents, fillers, lubricants, glidants, disintegrants, polishagents, suspending agents, dispersing agents, plasticizers.

In certain embodiments, the star macromolecule may be suitable in paperapplications, including but not limited to, coatings, dispersion fortissue and thin papers, filler retention and drainage enhancement,flocculation and pitch control, grease-proof coatings, adhesives,release coatings, surface sizing, sizes for gloss and ink holdout, tailtie and pickup adhesives for papermaking, deinking of recycled papers inflotation, washing and enzymatic processes.

In certain embodiments, the star macromolecule may be suitable inagricultural applications, including but not limited to, animal feed,dispersing agents, drift control, encapsulation, seed coatings, seedtape, spray adherents, water-based sprays and spray emulsions,water-soluble packaging, herbicides, insecticides.

In certain embodiments, the star macromolecule may be suitable in otherapplications including but not limited to, water- and solvent-basedcoating compositions, water- and solvent-based lubricants, water- andsolvent-based viscosity index modifiers, paints, plasticizers,firefighting, anti-fogs agents, antifoaming agents, antifreezesubstances, ski and snowboard waxes, laxatives, corrosion inhibitors,detergents, dental impression materials, dental fillers, ceramic andbrick forming, prepolymers such as polyols for use in polyesters,polyurethanes, polycarbonates. For rheology modifier applications,characteristics are high gel strength, stability in the presence of saltand increased temperatures, high shear thinning characteristics, formsversatile low viscosity soluble concentrations, and synergisticinteractions with added agents to adjust their rheology profile tooptimize properties such as sedimentation, flow and leveling, sagging,spattering, etc.

In certain embodiments, the star macromolecule may be suitable to storeand/or release in controlled rate small molecules. “Small molecules” mayinclude UV absorbers, minerals, dyes, pigments, solvents, surfactants,metal ions, salts, or oils. These small molecules may be stored, forexample, inside the core of the star macromolecule or among theplurality of polymeric arms, and then released. For example, a smallmolecule may have some affinity to the core or may be soluble in thecore environment. Higher affinity of a small molecule to the core (orpolymeric arms) may result in a lower rate of release from the starmacromolecule. The affinity may be increased or decreased throughnon-covalent forces, such as ionic, H-bonding, electrostatic,hydrophobic, coordination and metal chelating interactions.

Embodiment A1

A surfactant-system thickening macromolecule for increasing theviscosity of a surfactant-containing system, comprising:

-   -   a) a core;    -   b) at least one first polymeric arm, comprising a hydrophilic        polymeric segment covalently attached to the core; and    -   c) at least one second polymeric arm, comprising:        -   i) a hydrophilic polymeric segment covalently attached to            the core; and        -   ii) a further segment covalently attached to the hydrophilic            polymeric segment, wherein the further segment is comprised            of at least one monomeric residue of a polymerized            surfactant-system thickening monomer comprising a C₆ or            greater alkyl acrylate; C₆ or greater alkenyl acrylate; C₆            or greater alkyl alkyl acrylate; C₆ or greater alkenyl alkyl            acrylate; C₆ or greater alkyl acrylamide; C₆ or greater            alkenyl acrylamide; C₆ or greater alkyl alkyl acrylamide; C₆            or greater alkenyl alkyl acrylamide; C₂ or greater alkyl            vinyl ether; C₂ or greater alkenyl vinyl ether, C₁ or            greater alkyl allyl ether, or C₁ or greater alkenyl allyl            ether.

Embodiment A2

The macromolecule of Embodiment A1, wherein the at least one polymerizedsurfactant-system thickening monomeric residue comprises a C₆ or greateralkyl acrylate; C₆ or greater alkyl alkyl acrylate; C₆ or greater alkylacrylamide; C₆ or greater alkyl alkyl acrylamide; C₂ or greater alkylvinyl ether; or C₁ or greater alkyl allyl ether.

Embodiment A3

The macromolecule of Embodiments A1 or A2, wherein the at least onepolymerized surfactant-system thickening monomeric residue comprises aC₆₋₄₀ alkyl acrylate; C₆₋₄₀ alkyl alkyl acrylate; C₆₋₄₀ alkylacrylamide; C₆₋₄₀ alkyl alkyl acrylamide; C₂₋₄₀ alkyl vinyl ether; orC₁₋₄₀ alkyl allyl ether.

Embodiment A4

The macromolecule of any one of Embodiments A1-A3, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₁₃ or greater alkyl acrylate; C₁₁ or greater alkyl alkyl acrylate;C₁₉ or greater alkyl acrylamide; C₁₃ or greater alkyl alkyl acrylamide;C₂ or greater alkyl vinyl ether, or C₁ or greater alkyl allyl ether.

Embodiment A5

The macromolecule of any one of Embodiments A1-A4, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₁₃₋₄₀ alkyl acrylate; C₁₁₋₄₀ alkyl alkyl acrylate; C₁₉₋₄₀ alkylacrylamide; C₁₃₋₄₀ alkyl alkyl acrylamide; C₂₋₄₀ alkyl vinyl ether; orC₁₋₄₀ alkyl allyl ether.

Embodiment A6

The macromolecule of any one of Embodiments A1-A5, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₁₄ or greater alkyl acrylate; C₁₄ or greater alkyl alkyl acrylate;C₁₉ or greater alkyl acrylamide; C₁₄ or greater alkyl alkyl acrylamide;C₆ or greater alkyl vinyl ether, or C₆ or greater alkyl allyl ether.

Embodiment A7

The macromolecule of any one of Embodiments A1-A6, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₁₆ or greater alkyl acrylate; C₁₆ or greater alkyl alkyl acrylate;C₁₉ or greater alkyl acrylamide; C₁₆ or greater alkyl alkyl acrylamide;C₁₂ or greater alkyl vinyl ether; or C₁₂ or greater alkyl allyl ether.

Embodiment A8

The macromolecule of any one of Embodiments A1-A7, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₁₈ or greater alkyl acrylate; C₁₈ or greater alkyl alkyl acrylate;C₁₉ or greater alkyl acrylamide; C₁₈ or greater alkyl alkyl acrylamide;C₁₈ or greater alkyl vinyl ether; or C₁₈ or greater alkyl allyl ether.

Embodiment A9

The macromolecule of any one of Embodiments A1-A8, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa saturated fatty alkyl pendant moiety.

Embodiment A10

The macromolecule of Embodiment A9, wherein the saturated fatty alkylpendant moiety is: tridecyl, isotridecyl, myristyl, pentadecyl, cetyl,palmityl, heptadecyl, stearyl, nonadecyl, arachidyl, heneicosyl,behenyl, lignoceryl, ceryl (heptacosanyl), montanyl, nonacosanyl,myricyl, dotriacontanyl, geddyl, or cetostearyl pendant moiety.

Embodiment A11

The macromolecule of Embodiments A9 or A10, wherein the saturated fattyalkyl pendant moiety is a stearyl pendant moiety.

Embodiment A12

The macromolecule of any one of Embodiments A1-A11, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₆ or greater alkenyl acrylate; C₆ or greater alkenyl alkyl acrylate;C₆ or greater alkenyl acrylamide; C₆ or greater alkenyl alkylacrylamide; C₆ or greater alkenyl vinyl ether; or C₆ or greater alkenylallyl ether.

Embodiment A13

The macromolecule of any one of Embodiments A1-A12, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₆₋₄₀ alkenyl acrylate; C₆₋₄₀ alkenyl alkyl acrylate; C₆₋₄₀ alkenylacrylamide; C₆₋₄₀ alkenyl alkyl acrylamide; C₆₋₄₀ alkenyl vinyl ether;or C₆₋₄₀ alkenyl allyl ether.

Embodiment A14

The macromolecule of any one of Embodiments A1-A13, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₈ or greater alkenyl acrylate; C₈ or greater alkenyl alkyl acrylate;C₈ or greater alkenyl acrylamide; C₈ or greater alkenyl alkylacrylamide; C₈ or greater alkenyl vinyl ether; or C₈ or greater alkenylallyl ether.

Embodiment A15

The macromolecule of any one of Embodiments A1-A14, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₁₀ or greater alkenyl acrylate; C₁₀ or greater alkenyl alkylacrylate; C₁₀ or greater alkenyl acrylamide; C₁₀ or greater alkenylalkyl acrylamide; C₁₀ or greater alkenyl vinyl ether, or C₁₀ or greateralkenyl allyl ether.

Embodiment A16

The macromolecule of any one of Embodiments A1-A15, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₁₂ or greater alkenyl acrylate; C₁₂ or greater alkenyl alkylacrylate; C₁₂ or greater alkenyl acrylamide; C₁₂ or greater alkenylalkyl acrylamide; C₁₂ or greater alkenyl vinyl ether, or C₁₂ or greateralkenyl allyl ether.

Embodiment A17

The macromolecule of any one of Embodiments A1-A16, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₁₄ or greater alkenyl acrylate; C₁₄ or greater alkenyl alkylacrylate; C₁₄ or greater alkenyl acrylamide; C₁₄ or greater alkenylalkyl acrylamide; C₁₄ or greater alkenyl vinyl ether, or C₁₄ or greateralkenyl allyl ether.

Embodiment A18

The macromolecule of any one of Embodiments A1-A17, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesa C₁₈ or greater alkenyl acrylate; C₁₈ or greater alkenyl alkylacrylate; C₁₈ or greater alkenyl acrylamide; C₁₈ or greater alkenylalkyl acrylamide; C₁₈ or greater alkenyl vinyl ether, or C₁₈ or greateralkenyl allyl ether.

Embodiment A19

The macromolecule of any one of Embodiments A1-A18, wherein the alkenylgroup is a mono-, di-, tri, tetra, penta, or hexa-alkenyl group.

Embodiment A20

The macromolecule of any one of Embodiments A1-A19, wherein the at leastone polymerized surfactant-system thickening monomeric residue comprisesan unsaturated fatty alkyl pendant moiety.

Embodiment A21

The macromolecule of Embodiment A20, wherein the unsaturated fatty alkylpendant moiety is mono-unsaturated or poly-unsaturated.

Embodiment A22

The macromolecule of Embodiments A20 or A21, wherein thepoly-unsaturated fatty alkyl pendant moiety is a di-, tri, tetra, penta,or hexa-unsaturated fatty alkyl pendant moiety.

Embodiment A23

The macromolecule of any one of Embodiments A20-A22, wherein theunsaturated fatty alkyl pendant moiety is: myristoleyl, palmitoleyl,sapienyl, oleyl, elaidyl, vaccenyl, linoleyl, linoelaidyl, α-linolenyl,arachidonyl, eicosapentaenoyl, erucyl, or docosahexaenoyl pendantmoiety.

Embodiment A24

The macromolecule of any one of Embodiments A1-A23, wherein the at leastone polymerized surfactant-system thickening monomeric residue isrepresented by Formula I-V:

wherein:

-   -   R¹, R², and R³ independently represent hydrogen, methyl, ethyl,        or C₃₋₁₈ alkyl, for example C₃₋₆ alkyl, C₆₋₁₂ alkyl, or C₁₂₋₁₈        alkyl; wherein the alkyl may be branched or unbranched, linear        or cyclic, and may be optionally substituted with one or more        halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol);    -   R⁴ and R⁷ independently represent C₁₃ or greater alkyl, —C₆ or        greater alkyl-(O—C₁₋₆ alkyl)_(n), C₆ or greater alkenyl, or C₆        or greater alkenyl-(O—C₁₋₆ alkyl)_(n); or when R³ is C₁ or        greater, then R⁴ may independently represent C₁₁ or greater        alkyl, —C₆ or greater alkyl —(O—C₁₋₆ alkyl)_(n), C₆ or greater        alkenyl, or C₆ or greater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein        each alkyl portion independently may be branched or unbranched,        linear or cyclic, saturated or unsaturated, and may be        optionally substituted with one or more halogens, C₁₋₆ alkoxy        groups, or poly(ethylene glycol);    -   R⁵ independently represents C₁₉ or greater alkyl, —C₆ or greater        alkyl —(O—C₁₋₆ alkyl)_(n), C₆ or greater alkenyl, or C₆ or        greater alkenyl-(O—C₁₋₆ alkyl)_(n); or when R⁶ is C₁ or greater,        then R⁵ may independently represent C₁₃ or greater alkyl, —C₆ or        greater alkyl —(O—C₁₋₆ alkyl)_(n), C₆ or greater alkenyl, or C₆        or greater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkyl        portion independently may be branched or unbranched, linear or        cyclic, saturated or unsaturated, and may be optionally        substituted with one or more halogens, C₁₋₆ alkoxy groups, or        poly(ethylene glycol);    -   R⁶ independently represents hydrogen, C₁₋₁₈ alkyl, —C₁₋₁₈        alkyl-(O—C₁₋₆ alkyl)_(n), or is R⁴, or is R⁵; wherein each alkyl        portion independently may be branched or unbranched, linear or        cyclic, saturated or unsaturated, and may be optionally        substituted with one or more halogens, C₁₋₆ alkoxy groups, or        poly(ethylene glycol);    -   R⁸ independently represents C₂ or greater alkyl, —C₂ or greater        alkyl-(O—C₁₋₆ alkyl)_(n), C₃ or greater alkenyl, —C₃ or greater        alkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkyl portion        independently may be branched or unbranched, linear or cyclic,        saturated or unsaturated, and may be optionally substituted with        one or more halogens, C₁₋₆ alkoxy groups, or poly(ethylene        glycol);    -   R⁹ independently represents C₁ or greater alkyl, —C₁ or greater        alkyl-(O—C₁₋₆ alkyl)_(n), C₃ or greater alkenyl, —C₃ or greater        alkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkyl portion        independently may be branched or unbranched, linear or cyclic,        saturated or unsaturated, and may be optionally substituted with        one or more halogens, C₁₋₆ alkoxy groups, or poly(ethylene        glycol); or    -   R⁴, R⁵, R⁷, R⁸, R⁹ independently represent a hydrophobic portion        of a surfactant, a hydrophobic portion of a lipid, or a        hydrophobic portion of a fatty alcohol;    -   A¹, A², A³ and A⁴ independently represent CH, CR¹⁰, or N,        wherein at least two of A¹, A², A³ and A⁴ is CH or CR¹⁰;    -   R¹⁰ independently represents hydrogen, C₁₋₁₀ alkyl, halogen,        hydroxyl, C₁₋₁₀ alkoxy; wherein the alkyl or alkoxy may be        branched or unbranched, linear or cyclic, and may be optionally        substituted with one or more halogens, C₁₋₆ alkoxy groups, or        poly(ethylene glycol);    -   Y independently represents a covalent bond, —O—, —S—, —N(H)—,        —N(R¹)—, —(CO)—, —S(O)—, —S(O)₂—, —S(O)₂N(R¹)—, —(CO)N(R¹)—,        —N(R¹)—(CO)—, —(CO)O—, or —O—(CO)—;    -   L¹ independently represents a covalent bond, ethylene glycol,        poly(ethylene glycol), polyether, polyamide, C₁₋₆ alkyl,        —(CO)N(R¹)—, —N(R¹)—(CO)—, —(CO)O—, —O—(CO)—, or combinations        thereof, or is independently absent; or    -   L¹ independently represents a hydrophilic portion of a        surfactant, a hydrophilic portion of a lipid, or a hydrophilic        portion of a fatty alcohol;    -   L² independently represents (CH₂)₁₋₄₀, C₁₋₄₀ alkyl, (O—C₂₋₆        alkyl)_(n), or (C₂₋₆ alkyl)-(O—C₂₋₆ alkyl)_(n); wherein the        alkyl may be branched or unbranched, linear or cyclic, and may        be optionally substituted with one or more halogens, C₁₋₆ alkoxy        groups, or poly(ethylene glycol); and    -   n independently represents a value in the range of 1-1000.

Embodiment A25

The macromolecule of any one of Embodiments A1-A24, wherein thesurfactant-system thickening macromolecule comprises a plurality of theat least first polymeric arm.

Embodiment A26

The macromolecule of any one of Embodiments A1-A25, wherein thesurfactant-system thickening macromolecule comprises a plurality of theat least second polymeric arm.

Embodiment A27

The macromolecule of any one of Embodiments A1-A26, wherein thesurfactant-system thickening macromolecule comprises a plurality of theat least first polymeric arm and a plurality of the at least secondpolymeric arm.

Embodiment A28

The macromolecule of any one of Embodiments A1-A27, wherein the at leastone second polymeric arm has a molecular weight of greater than 5,000g/mol.

Embodiment A29

The macromolecule of any one of Embodiments A1-A28, wherein the core isa crosslinked polymeric core.

Embodiment A30

The macromolecule of any one of Embodiments A1-A29, wherein the core isa hydrophobic crosslinked polymeric core.

Embodiment A31

The macromolecule of any one of Embodiments A1-A30, wherein thehydrophilic polymeric segment of the at least one first polymeric arm iscomprised of a plurality of polymerized hydrophilic monomers.

Embodiment A32

The macromolecule of any one of Embodiments A1-A31, wherein thehydrophilic polymeric segment of the at least one first polymeric arm iscomprised of between 5 and 2000 monomeric residues of polymerizedhydrophilic monomers.

Embodiment A33

The macromolecule of any one of Embodiments A1-A32, wherein the furthersegment is comprised of a plurality of the at least one polymerizedsurfactant-system thickening monomeric residues.

Embodiment A34

The macromolecule of any one of Embodiments A1-A33, wherein the furthersegment of the at least one second polymeric arm is comprised of between1 and 500 monomeric residues of polymerized surfactant-system thickeningmonomers.

Embodiment A35

The macromolecule of any one of Embodiments A1-A34, wherein thehydrophilic polymeric segment of the at least one second polymeric armis comprised of between 10 and 5000 monomeric residues of polymerizedhydrophilic monomers.

Embodiment A36

The macromolecule of any one of Embodiments A1-A35, wherein the furthersegment is the distal segment of the at least second polymeric arm.

Embodiment A37

The macromolecule of any one of Embodiments A1-A36, wherein the at leastsecond polymeric arm consists of the hydrophilic polymeric segment andthe further segment.

Embodiment A38

The macromolecule of any one of Embodiments A1-A37, wherein themonomeric residues of polymerized hydrophilic monomers of said at leastone second polymeric arm are proximal to the core.

Embodiment A39

The macromolecule of any one of Embodiments A1-A38, wherein the at leastone second polymeric arm comprises more of the monomeric residues ofpolymerized hydrophilic monomers than the monomeric residues ofpolymerized surfactant-system thickening monomers.

Embodiment A40

The macromolecule of any one of Embodiments A1-A39, wherein the at leastone second polymeric arm comprises in the range of between 2 and 1000times more of the monomeric residues of polymerized hydrophilic monomersthan the monomeric residues of polymerized surfactant-system thickeningmonomers.

Embodiment A41

The macromolecule of any one of Embodiments A1-A40, wherein the at leastone second polymeric arm comprises 2 times, 3 times, 4 times, 5 times,10 times, 50 times, 100 times, or greater than 100 times, more of themonomeric residues of polymerized hydrophilic monomers than themonomeric residues of polymerized surfactant-system thickening monomers.

Embodiment A42

The macromolecule of any one of Embodiments A1-A41, wherein thesurfactant-system thickening macromolecule, optionally, furthercomprises at least one third polymeric arm, comprising a polymericsegment comprised of monomeric residues of polymerized hydrophobicmonomers, a polymeric segment comprised of monomeric residues ofpolymerized hydrophilic monomers, or both.

Embodiment A43

The macromolecule of Embodiment A42, wherein the surfactant-systemthickening macromolecule further comprises the at least one thirdpolymeric arm.

Embodiment A44

The macromolecule of Embodiments A42 or A43, wherein the at least onethird polymeric arm comprises the polymeric segment comprised ofmonomeric residues of polymerized hydrophobic monomers.

Embodiment A45

The macromolecule of Embodiment A45, wherein the polymeric segmentcomprised of monomeric residues of polymerized hydrophobic monomers ofthe at least one third polymeric arm is a hydrophobic polymeric segment.

Embodiment A46

The macromolecule of any one of Embodiments A43-A45, wherein the atleast one third polymeric arm comprises the polymeric segment comprisedof monomeric residues of polymerized hydrophilic monomers.

Embodiment A47

The macromolecule of Embodiment A46, wherein the polymeric segmentcomprised of monomeric residues of polymerized hydrophilic monomers ofthe at least one third polymeric arm is a hydrophilic polymeric segment.

Embodiment A48

The macromolecule of any one of Embodiments A43-A47, wherein thesurfactant-system thickening macromolecule comprises a plurality of theat least one third polymeric arm.

Embodiment A49

The macromolecule of any one of Embodiments A43-A48, wherein thehydrophobic polymeric segment of the at least one third polymeric arm iscomprised of a plurality of the monomeric residues of polymerizedhydrophobic monomers.

Embodiment A50

The macromolecule of any one of Embodiments A43-A49, wherein thehydrophobic polymeric segment of the at least one third polymeric arm iscomprised of between 1 and 500 monomeric residues of polymerizedhydrophobic monomers.

Embodiment A51

The macromolecule of any one of Embodiments A43-A50, wherein themonomeric residues of polymerized hydrophobic monomers of said at leastone third polymeric arm are distal to the core.

Embodiment A52

The macromolecule of any one of Embodiments A43-A51, wherein thehydrophilic polymeric segment of the at least one third polymeric arm iscomprised of a plurality of the monomeric residues of polymerizedhydrophilic monomers.

Embodiment A53

The macromolecule of any one of Embodiments A43-A52, wherein thehydrophilic polymeric segment of the at least one third polymeric arm iscomprised of between 1 and 5,000 monomeric residues of polymerizedhydrophilic monomers.

Embodiment A54

The macromolecule of any one of Embodiments A43-A53, wherein themonomeric residues of polymerized hydrophilic monomers of said at leastone third polymeric arm are proximal to the core.

Embodiment A55

The macromolecule of any one of Embodiments A43-A54, wherein thehydrophilic polymeric segment of the at least one third polymeric arm iscovalently attached to the core.

Embodiment A56

The macromolecule of any one of Embodiments A43-A55, wherein the atleast one third polymeric arm consists of the hydrophilic polymericsegment and the hydrophobic polymeric segment.

Embodiment A57

The macromolecule of any one of Embodiments A43-A56, wherein the atleast one third polymeric arm comprises more of the monomeric residuesof polymerized hydrophilic monomers than the monomeric residues ofpolymerized hydrophobic monomers.

Embodiment A58

The macromolecule of any one of Embodiments A43-A57, wherein the atleast one third polymeric arm comprises in the range of between 2 and1000 times more of the monomeric residues of polymerized hydrophilicmonomers than the monomeric residues of polymerized hydrophobicmonomers.

Embodiment A59

The macromolecule of any one of Embodiments A43-A58, wherein the atleast one third polymeric arm comprises 2 times, 3 times, 4 times, 5times, 10 times, 50 times, 100 times, or greater than 100 times, more ofthe monomeric residues of polymerized hydrophilic monomers than themonomeric residues of polymerized hydrophobic monomers.

Embodiment A60

The macromolecule of any one of Embodiments A1-A59, wherein the ratio ofthe at least first polymeric arms to the at least second polymeric armsis in the range of between 40:1 and 1:40.

Embodiment A61

The macromolecule of any one of Embodiments A1-A60, wherein the ratio ofthe at least first polymeric arms to the at least third polymeric arms,the at least third polymeric arms to the at least second polymeric arms,and the at least first polymeric arms to the sum of the at least secondpolymeric arms and the at least third polymeric arms, are independentlyin the range of between 40:1 and 1:40.

Embodiment A62

The macromolecule of any one of Embodiments A1-A61, wherein thesurfactant-system thickening macromolecule is represented by Formula A:

[(P1)_(q1)]_(r)-Core-[(P3)_(q3)-(P2)_(q2)]_(s)  Formula A

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents the hydrophilic polymeric segment of        the at least first polymeric arm comprised of monomeric residues        of polymerized hydrophilic monomers;    -   P2 independently represents the further segment of the at least        second polymeric arm comprised of at least one monomeric residue        of a polymerized surfactant-system thickening monomer,    -   P3 independently represents the hydrophilic polymeric segment of        the at least second polymeric arm comprised of monomeric        residues of polymerized hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   r independently represents the number of the at least first        polymeric arms covalently attached to the Core; and    -   s independently represents the number of the at least second        polymeric arms covalently attached to the Core.

Embodiment A63

The macromolecule of Embodiment A62, wherein the ratio of r:s is in therange of between 40:1 and 1:40.

Embodiment A64

The macromolecule of any one of Embodiments A1-A63, wherein thesurfactant-system thickening macromolecule is represented by Formula B:

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents the hydrophilic polymeric segment of        the at least first polymeric arm comprised of monomeric residues        of polymerized hydrophilic monomers;    -   P2 independently represents the further segment of the at least        second polymeric arm comprised of at least one monomeric residue        of a polymerized surfactant-system thickening monomer,    -   P3 independently represents the hydrophilic polymeric segment of        the at least second polymeric arm comprised of monomeric        residues of polymerized hydrophilic monomers;    -   P4 independently represents the hydrophobic polymeric segment of        the at least third polymeric arm comprised of monomeric residues        of polymerized hydrophobic monomers;    -   P5 independently represents the hydrophilic polymeric segment of        the at least third polymeric arm comprised of monomeric residues        of polymerized hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   q4 independently represents the number of monomeric residues in        P4;    -   q5 independently represents the number of monomeric residues in        P5;    -   r independently represents the number of the at least first        polymeric arms covalently attached to the Core;    -   s independently represents the number of the at least second        polymeric arms covalently attached to the Core; and    -   t independently represents the number of the at least third        polymeric arms covalently attached to the Core.

Embodiment A65

The macromolecule of Embodiment A64, wherein the ratio of r:s, and, if tis not zero, the ratio of r:t, t:s, and r:(s+t), are independently inthe range of between 40:1 and 1:40.

Embodiment A66

The macromolecule of any one of Embodiments A62-A65, wherein q1 has avalue between 5 and 2000.

Embodiment A67

The macromolecule of any one of Embodiments A62-A66, wherein q2 has avalue between 1 and 500.

Embodiment A68

The macromolecule of any one of Embodiments A62-A67, wherein q3 has avalue between 10 and 5000.

Embodiment A69

The macromolecule of any one of Embodiments A62-A68, wherein q4 has avalue between 1 and 500.

Embodiment A70

The macromolecule of any one of Embodiments A62-A69, wherein q5 has avalue between 10 and 5000.

Embodiment A71

The macromolecule of any one of Embodiments A62-A70, wherein r has avalue in the range of from 1 to 1000.

Embodiment A72

The macromolecule of any one of Embodiments A62-A71, wherein s has avalue in the range of from 1 to 1000.

Embodiment A73

The macromolecule of any one of Embodiments A62-A72, wherein t has avalue in the range of from 0 to 1000.

Embodiment A74

The macromolecule of any one of Embodiments A62-A73, wherein q3 isgreater than q2.

Embodiment A75

The macromolecule of any one of Embodiments A62-A74, wherein q3 is inthe range of between 2 and 1000 times greater than q2.

Embodiment A76

The macromolecule of any one of Embodiments A62-A75, wherein q3 is 2times, 3 times, 4 times, 5 times, 10 times, 50 times, 100 times, orgreater than 100 times, greater than q2.

Embodiment A77

The macromolecule of any one of Embodiments A62-A76, wherein q5 isgreater than q4.

Embodiment A78

The macromolecule of any one of Embodiments A62-A77, wherein q5 is inthe range of between 2 and 1000 times greater than q4.

Embodiment A79

The macromolecule of any one of Embodiments A62-A78, wherein q5 is 2times, 3 times, 4 times, 5 times, 10 times, 50 times, 100 times, orgreater than 100 times, greater than q4.

Embodiment A80

The macromolecule of any one of Embodiments A62-A79, wherein thepolymeric segment P1, P3, or P5 is a homopolymeric segment, acopolymeric segment, a block copolymeric segment, a blocky copolymericsegment, a gradient copolymeric segment, or a random copolymericsegment.

Embodiment A81

The macromolecule of any one of Embodiments A62-A80, wherein thepolymeric segment P2 or P4 is a homopolymeric segment, a copolymericsegment, a block copolymeric segment, a blocky copolymeric segment, agradient copolymeric segment, or a random copolymeric segment.

Embodiment A82

The macromolecule of any one of Embodiments A1-A81, wherein a portion ofthe further segment is represented by Formula E:

wherein:

-   -   R¹¹, R¹², R¹³ independently represent hydrogen, methyl, ethyl,        or C₃₋₁₈ alkyl, for example C₃₋₆ alkyl, C₆₋₁₂ alkyl, or C₁₂₋₁₈        alkyl; wherein the alkyl may be branched or unbranched, linear        or cyclic, and may be optionally substituted with one or more        halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol);    -   R¹⁴ independently represents C₁₋₁₂ hydrocarbyl, —C₁₋₁₂        hydrocarbyl-(O—C₁₋₆ hydrocarbyl)_(w), —C₁₋₁₂        hydrocarbyl-((CO)O—C₁₋₆ hydrocarbyl)_(w), —C₁₋₁₂        hydrocarbyl-((CO)NH—C₁₋₆ hydrocarbyl)_(w); wherein each        hydrocarbyl portion independently may be branched or unbranched,        linear or cyclic, saturated (alkyl) or unsaturated (alkenyl),        and may be optionally substituted with one or more halogens,        C₁₋₆ alkoxy groups, or poly(ethylene glycol);    -   R¹⁵ independently represents C₁₃₋₄₀ hydrocarbyl, —C₁₃₋₄₀        hydrocarbyl-(O—C₁₋₆ hydrocarbyl)_(w), —C₁₃₋₄₀        hydrocarbyl-((CO)O—C₁₋₆ hydrocarbyl)_(w), C₁₃₋₄₀        hydrocarbyl-((CO)NH—C₁₋₆ alkyl)_(w); wherein each hydrocarbyl        portion independently may be branched or unbranched, linear or        cyclic, saturated (alkyl) or unsaturated (alkenyl), and may be        optionally substituted with one or more halogens, C₁₋₆ alkoxy        groups, or poly(ethylene glycol); or a hydrophobic moiety of a        surfactant, a hydrophobic moiety of a lipid, or a hydrophobic        moiety of a fatty alcohol;    -   Y represents a covalent bond, ethylene glycol, poly(ethylene        glycol), polyether, polyamide, C₁₋₆ alkyl, or combinations        thereof, or is independently absent;    -   m independently represents a value in the range of 1-500;    -   n independently represents a value in the range of 1-500; and    -   w independently represents a value in the range of 1-1000.

Embodiment A83

The macromolecule of Embodiment A82, wherein the portion of the at leastone second polymeric arm represented by Formula E is a copolymericsegment, a block copolymeric segment, a blocky copolymeric segment, agradient copolymeric segment, or a random copolymeric segment.

Embodiment A84

The macromolecule of any one of Embodiments A1-A83, wherein the furthersegment is a polymeric segment.

Embodiment A85

The macromolecule of Embodiment A84, wherein the further segment is ahomopolymeric segment, a copolymeric segment, a block copolymericsegment, a blocky copolymeric segment, a gradient copolymeric segment,or a random copolymeric segment.

Embodiment A86

The macromolecule of any one of Embodiments A1-A85, wherein the furthersegment is a surfactant-system thickening polymeric segment.

Embodiment A87

The macromolecule of Embodiment A86, wherein the surfactant-systemthickening polymeric segment is a homopolymeric segment, a copolymericsegment, a block copolymeric segment, a blocky copolymeric segment, agradient copolymeric segment, or a random copolymeric segment.

Embodiment A88

The macromolecule of any one of Embodiments A1-A87, wherein thesurfactant-system thickening macromolecule has a molecular weight (Mn)in the range of between 5,000 g/mol and 10,000,000 g/mol.

Embodiment A89

The macromolecule of any one of Embodiments A1-A88, wherein thesurfactant-system thickening macromolecule has a molecular weight (Mn)of greater than 100,000 g/mol.

Embodiment A90

The macromolecule of any one of Embodiments A1-A89, wherein thesurfactant-system thickening macromolecule has a molecular weight (Mn)in the range of between 100,000 g/mol and 2,000,000 g/mol.

Embodiment A91

The macromolecule of any one of Embodiments A1-A90, wherein themolecular weight (Mn) of the at least one polymeric arm is between 1,000g/mol to 250,000 g/mol.

Embodiment A92

The macromolecule of any one of Embodiments A1-A91, wherein themolecular weight (Mn) of the at least one polymeric arm is between10,000 g/mol and 200,000 g/mol.

Embodiment A93

The macromolecule of any one of Embodiments A1-A92, wherein thesurfactant-system thickening macromolecule is a water soluble mikto starmacromolecule.

Embodiment A94

The macromolecule of any one of Embodiments A1-A93, wherein when 0.4 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamicviscosity of at least 5,000 cP at a shear rate of 2.2 s⁻¹ at 25° C.,according to the Thickening and Shear Thinning in Water Test.

Embodiment A95

The macromolecule of Embodiment A94, wherein the dynamic viscosity is atleast 10,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theThickening and Shear Thinning in Water Test.

Embodiment A96

The macromolecule of Embodiments A94 or A95, wherein the macromoleculefurther has a shear thinning value of at least 80%, according to theThickening and Shear Thinning in Water Test.

Embodiment A97

The macromolecule of any one of Embodiments A1-A96, wherein when 2.0 wt.% of the macromolecule forms a homogeneous gel, the gel has a dynamicviscosity of at least 500 cP at a shear rate of 2.2 s⁻¹ at 25° C.,according to the SLES Surfactant Compatibility Test.

Embodiment A98

The macromolecule of Embodiment A97, wherein the dynamic viscosity is atleast 1,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theSLES Surfactant Compatibility Test.

Embodiment A99

The macromolecule of Embodiment A98, wherein the dynamic viscosity is atleast 2,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theSLES Surfactant Compatibility Test.

Embodiment A100

The macromolecule of Embodiment A99, wherein the dynamic viscosity is atleast 3,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theSLES Surfactant Compatibility Test.

Embodiment A101

The macromolecule of Embodiment A100, wherein the dynamic viscosity isat least 4,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theSLES Surfactant Compatibility Test.

Embodiment A102

The macromolecule of any one of Embodiments A97-A101, wherein themacromolecule further has a shear thinning value of at least 75%,according to the SLES Surfactant Compatibility Test.

Embodiment A103

The macromolecule of any one of Embodiments A1-A102, wherein when 2.0wt. % of the macromolecule forms a homogeneous gel, the gel has adynamic viscosity of at least 5,000 cP at a shear rate of 2.2 s⁻¹ at 25°C., according to the Hybrid SLES-CH Surfactant Compatibility Test.

Embodiment A104

The macromolecule of Embodiment A103, wherein the dynamic viscosity isat least 10,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according tothe Hybrid SLES-CH Surfactant Compatibility Test.

Embodiment A105

The macromolecule of Embodiment A104, wherein the dynamic viscosity isat least 15,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according tothe Hybrid SLES-CH Surfactant Compatibility Test.

Embodiment A106

The macromolecule of Embodiment A105, wherein the dynamic viscosity isat least 18,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according tothe Hybrid SLES-CH Surfactant Compatibility Test.

Embodiment A107

The macromolecule of Embodiment A106, wherein the dynamic viscosity isat least 20,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according tothe Hybrid SLES-CH Surfactant Compatibility Test.

Embodiment A108

The macromolecule of any one of Embodiments A103-A107, wherein themacromolecule further has a shear thinning value of at least 35%,according to the Hybrid SLES-CH Surfactant Compatibility Test.

Embodiment A109

The macromolecule of any one of Embodiments A103-A107, wherein themacromolecule further has a shear thinning value of at least 40%,according to the Hybrid SLES-CH Surfactant Compatibility Test.

Embodiment A110

The macromolecule of any one of Embodiments A103-A107, wherein themacromolecule further has a shear thinning value of at least 50%,according to the Hybrid SLES-CH Surfactant Compatibility Test.

Embodiment A111

The macromolecule of any one of Embodiments A103-A107, wherein themacromolecule further has a shear thinning value of at least 70%,according to the Hybrid SLES-CH Surfactant Compatibility Test.

Embodiment A112

The macromolecule of any one of Embodiments A103-A107, wherein themacromolecule further has a shear thinning value of at least 80%,according to the Hybrid SLES-CH Surfactant Compatibility Test.

Embodiment A113

The macromolecule of any one of Embodiments A1-A112, wherein when 1.5wt. % of the macromolecule forms a homogeneous gel, the gel has adynamic viscosity of at least 2,000 cP at a shear rate of 2.2 s⁻¹ at 25°C., according to the Hybrid CB-SLES Surfactant Compatibility Test.

Embodiment A114

The macromolecule of Embodiment A113, wherein the dynamic viscosity isat least 3,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theHybrid CB-SLES Surfactant Compatibility Test.

Embodiment A115

The macromolecule of Embodiment A113, wherein the dynamic viscosity isat least 5,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theHybrid CB-SLES Surfactant Compatibility Test.

Embodiment A116

The macromolecule of Embodiment A113, wherein the dynamic viscosity isat least 7,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theHybrid CB-SLES Surfactant Compatibility Test.

Embodiment A117

The macromolecule of Embodiment A113, wherein the dynamic viscosity isat least 10,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according tothe Hybrid CB-SLES Surfactant Compatibility Test.

Embodiment A118

The macromolecule of Embodiment A113, wherein the dynamic viscosity isat least 15,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according tothe Hybrid CB-SLES Surfactant Compatibility Test.

Embodiment A119

The macromolecule of any one of Embodiments A1-A118, wherein when 1.5wt. % of the macromolecule forms a homogeneous gel, the gel has adynamic viscosity of at least 2,000 cP at a shear rate of 0.22 s⁻¹ at25° C., according to the Hybrid CB-SLES Surfactant with NaClCompatibility Test.

Embodiment A120

The macromolecule of Embodiment A119, wherein the dynamic viscosity isat least 4,000 cP at a shear rate of 0.22 s⁻¹ at 25° C., according tothe Hybrid CB-SLES Surfactant with NaCl Compatibility Test.

Embodiment A121

The macromolecule of Embodiment A119, wherein the dynamic viscosity isat least 6,000 cP at a shear rate of 0.22 s⁻¹ at 25° C., according tothe Hybrid CB-SLES Surfactant with NaCl Compatibility Test.

Embodiment A122

The macromolecule of Embodiment A119, wherein the dynamic viscosity isat least 8,000 cP at a shear rate of 0.22 s⁻¹ at 25° C., according tothe Hybrid CB-SLES Surfactant with NaCl Compatibility Test.

Embodiment A123

The macromolecule of Embodiment A119, wherein the dynamic viscosity isat least 10,000 cP at a shear rate of 0.22 s⁻¹ at 25° C., according tothe Hybrid CB-SLES Surfactant with NaCl Compatibility Test.

Embodiment A124

The macromolecule of Embodiment A119, wherein the dynamic viscosity isat least 15,000 cP at a shear rate of 0.22 s⁻¹ at 25° C., according tothe Hybrid CB-SLES Surfactant with NaCl Compatibility Test.

Embodiment A125

The macromolecule of Embodiment A119, wherein the mixture is treatedwith 10 wt. % NaCl, and the formed homogeneous gel has a dynamicviscosity of at least 2,500 cP at a shear rate of 0.22 s⁻¹ at 25° C.,according to the Hybrid CB-SLES Surfactant with NaCl Compatibility Test.

Embodiment A126

The macromolecule of Embodiment A119, wherein the mixture is treatedwith 10 wt. % NaCl, and the formed homogeneous gel has a dynamicviscosity of at least 5,000 cP at a shear rate of 0.22 s⁻¹ at 25° C.,according to the Hybrid CB-SLES Surfactant with NaCl Compatibility Test.

Embodiment A127

The macromolecule of Embodiment A119, wherein the mixture is treatedwith 10 wt. % NaCl, and the formed homogeneous gel has a dynamicviscosity of at least 10,000 cP at a shear rate of 0.22 s⁻¹ at 25° C.,according to the Hybrid CB-SLES Surfactant with NaCl Compatibility Test.

Embodiment A128

The macromolecule of any one of Embodiments A1-A127, wherein when 2.0wt. % of the macromolecule forms a homogeneous gel, the gel has adynamic viscosity of at least 15,000 cP at a shear rate of 2.2 s⁻¹ at25° C., according to the Ritabate 20 Surfactant Compatibility Test.

Embodiment A129

The macromolecule of Embodiment A128, wherein the dynamic viscosity isat least 20,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according tothe Ritabate 20 Surfactant Compatibility Test.

Embodiment A130

The macromolecule of Embodiment A128, wherein the dynamic viscosity isat least 25,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according tothe Ritabate 20 Surfactant Compatibility Test.

Embodiment A131

The macromolecule of Embodiment A128, wherein the dynamic viscosity isat least 30,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according tothe Ritabate 20 Surfactant Compatibility Test.

Embodiment A132

The macromolecule of any one of Embodiments A1-A131, wherein when 2.0wt. % of the macromolecule forms a homogeneous gel, the gel has adynamic viscosity of at least 1,500 cP at a shear rate of 2.2 s⁻¹ at 25°C., according to the APG Surfactant Compatibility Test.

Embodiment A133

The macromolecule of Embodiment A132, wherein the dynamic viscosity isat least 2,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theAPG Surfactant Compatibility Test.

Embodiment A134

The macromolecule of Embodiment A132, wherein the dynamic viscosity isat least 2,500 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theAPG Surfactant Compatibility Test.

Embodiment A135

The macromolecule of Embodiment A132, wherein the dynamic viscosity isat least 2,750 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theAPG Surfactant Compatibility Test.

Embodiment A136

The macromolecule of Embodiment A132, wherein the dynamic viscosity isat least 3,000 cP at a shear rate of 2.2 s⁻¹ at 25° C., according to theAPG Surfactant Compatibility Test.

Embodiment A137

The macromolecule of any one of Embodiments A1-A136, wherein when 0.4wt. % of the macromolecule forms a homogeneous gel, the gel has adynamic viscosity of at least 100,000 cP at a shear rate of 0.22 s⁻¹ at25° C., and has a Dynamic Viscosity at 80° C. that is at least 50%relative to the viscosity of the gel at 25° C., according to theTemperature Stability Test.

Embodiment A138

The macromolecule of Embodiment A137, wherein the dynamic viscosity at80° C. that is at least 60% relative to the viscosity of the gel at 25°C., according to the Temperature Stability Test.

Embodiment A139

The macromolecule of Embodiment A137, wherein the dynamic viscosity at80° C. that is at least 80% relative to the viscosity of the gel at 25°C., according to the Temperature Stability Test.

Embodiment A140

The macromolecule of Embodiment A137, wherein the dynamic viscosity at80° C. that is greater than the viscosity of the gel at 25° C.,according to the Temperature Stability Test.

Embodiment A141

The macromolecule of any one of Embodiments A1-A140, wherein when 1.5wt. % of the macromolecule forms a homogeneous gel, the gel has adynamic viscosity of at least 8,000 cP at an adjusted pH in the range ofbetween 4.5 to 6.5 at a shear rate of 0.22 s⁻¹ at 25° C., according tothe pH Efficiency Range in Hybrid CB/SLES Surfactant Test.

Embodiment A142

The macromolecule of Embodiment A141, wherein the dynamic viscosity isat least 15,000 cP at an adjusted pH in the range of between 4.5 to 6.5at a shear rate of 0.22 s⁻¹ at 25° C., according to the pH EfficiencyRange in Hybrid CB/SLES Surfactant Test.

Embodiment A143

The macromolecule of Embodiment A141, wherein the dynamic viscosity isat least 25,000 cP at an adjusted pH in the range of between 4.5 to 6.5at a shear rate of 0.22 s⁻¹ at 25° C., according to the pH EfficiencyRange in Hybrid CB/SLES Surfactant Test.

Embodiment A144

The macromolecule of Embodiment A141, wherein the dynamic viscosity isat least 50,000 cP at an adjusted pH in the range of between 4.5 to 6.5at a shear rate of 0.22 s⁻¹ at 25° C., according to the pH EfficiencyRange in Hybrid CB/SLES Surfactant Test.

Embodiment A145

The macromolecule of Embodiment A141, wherein the dynamic viscosity isat least 75,000 cP at an adjusted pH in the range of between 4.5 to 6.5at a shear rate of 0.22 s⁻¹ at 25° C., according to the pH EfficiencyRange in Hybrid CB/SLES Surfactant Test.

Embodiment A146

The macromolecule of any one of Embodiments A141-A145, wherein theadjusted pH is in the range of between 5 to 6 at a shear rate of 0.22s⁻¹ at 25° C., according to the pH Efficiency Range in Hybrid CB/SLESSurfactant Test.

Embodiment A147

The macromolecule of any one of Embodiments A1-A146, wherein when 0.4wt. % of the macromolecule forms a homogeneous gel, the gel has adynamic viscosity of at least 5,000 cP at an adjusted pH in the range ofbetween 5 to 12 at a shear rate of 0.22 s⁻¹ at 25° C., according to thepH Efficiency Range Test.

Embodiment A148

The macromolecule of Embodiment A147, wherein the dynamic viscosity isat least 25,000 cP at an adjusted pH in the range of between 5 to 12 ata shear rate of 0.22 s⁻¹ at 25° C., according to the pH Efficiency RangeTest.

Embodiment A149

The macromolecule of Embodiment A147, wherein the dynamic viscosity isat least 50,000 cP at an adjusted pH in the range of between 5 to 12 ata shear rate of 0.22 s⁻¹ at 25° C., according to the pH Efficiency RangeTest.

Embodiment A150

The macromolecule of Embodiment A147, wherein the dynamic viscosity isat least 75,000 cP at an adjusted pH in the range of between 5 to 12 ata shear rate of 0.22 s⁻¹ at 25° C., according to the pH Efficiency RangeTest.

Embodiment A151

The macromolecule of Embodiment A147, wherein the dynamic viscosity isat least 95,000 cP at an adjusted pH in the range of between 5 to 12 ata shear rate of 0.22 s⁻¹ at 25° C., according to the pH Efficiency RangeTest.

Embodiment A152

The macromolecule of any one of Embodiments A147-151, wherein theadjusted pH is in the range of between 6 to 7.

Embodiment A153

The macromolecule of any one of Embodiments A147-151, wherein theadjusted pH is in the range of between 7 to 8.

Embodiment A154

The macromolecule of any one of Embodiments A147-151, wherein theadjusted pH is in the range of between 8 to 10.

Embodiment A155

The macromolecule of any one of Embodiments A147-151, wherein theadjusted pH is in the range of between 8 to 9.

Embodiment A156

The macromolecule of any one of Embodiments A1-155, wherein thesurfactant is a nonionic surfactant, an anionic surfactant, anamphoteric surfactant, or a cationic surfactant.

Embodiment A157

The macromolecule of Embodiment A156, wherein the surfactant is anonionic surfactant.

Embodiment A158

The macromolecule of Embodiment A156, wherein the surfactant is a ananionic surfactant.

Embodiment A159

The macromolecule of Embodiment A156, wherein the surfactant is anamphoteric surfactant.

Embodiment A160

The macromolecule of Embodiment A156, wherein the surfactant is acationic surfactant.

Embodiment B1

A surfactant-modified star macromolecule, comprising:

-   -   i) a core;    -   ii) at least one first polymeric arm, comprising a hydrophilic        polymeric segment covalently attached to the core; and    -   iii) at least one second polymeric arm, comprising:        -   a) a hydrophilic polymeric segment covalently attached to            the core; and        -   b) a further segment comprising at least one pendant moiety            represented by

[L¹-G¹-L²-G²];

-   -    wherein:        -   G¹ independently represents a residue of a hydrophilic            moiety of the surfactant;        -   G² independently represents a residue of a hydrophobic            moiety of the surfactant;        -   L¹ independently represents a linking group or a covalent            bond, attaching G¹ to the further segment; and        -   L² independently represents a linking group or a covalent            bond, linking G¹ and G².

Embodiment B2

The surfactant-modified star macromolecule of Embodiment B1, wherein thefurther segment is the distal segment of the at least one secondpolymeric arm.

Embodiment B3

The surfactant-modified star macromolecule of Embodiments B1 or B2,wherein the at least one second polymeric arm extends beyond the atleast one first polymeric arm.

Embodiment B4

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B3, wherein at least a portion of the hydrophilic polymeric segmentof the at least one second polymeric arm extends beyond the distalportion of the at least one first polymeric arm.

Embodiment B5

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B4, wherein the proximal portion of the further segment extendsbeyond the distal portion of the at least one first polymeric arm.

Embodiment B6

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B5, wherein the further segment comprises a plurality of the at leastone pendant moieties.

Embodiment B7

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B6, wherein the further segment comprises in the range of between 1and 500 of the at least one pendant moieties.

Embodiment B8

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B7, wherein G² comprises a C₆ or greater alkyl moiety, afluorine-modified C₄ or greater alkyl moiety, or a C₆ or greater alkenylmoiety.

Embodiment B9

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B8, wherein G² comprises a C₁₃ or greater saturated fatty alkylmoiety, a C₁₂ or greater mono-unsaturated fatty alkyl moiety, or a C₁₂or greater poly-unsaturated fatty alkyl moiety.

Embodiment B10

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B9, wherein G² comprises a C₁₄ or greater saturated fatty alkylmoiety.

Embodiment B11

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B10, wherein G² comprises a C₁₆ or greater saturated fatty alkylmoiety.

Embodiment B12

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B11, wherein G² comprises a C₁₈ or greater saturated fatty alkylmoiety.

Embodiment B13

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B12, wherein G² comprises the hydrophobic moiety of a commerciallysuitable surfactant and/or registered in Toxic Substances Control Act(TSCA).

Embodiment B14

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B13, wherein L¹ is a covalent bond, G¹ is an ester moiety, and G²comprises a C₁₈ or greater saturated fatty alkyl moiety.

Embodiment B15

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B14, wherein the G² further comprises an aryl moiety, an ethermoiety, a carbonyl moiety, or an unsaturated alkyl moiety.

Embodiment B16

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B15, wherein the surfactant-modified star macromolecule comprises aplurality of the at least one first polymeric arm and a plurality of theat least one second polymeric arm.

Embodiment B17

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B16, wherein each of the at least one second polymeric arms comprisein the range of between 1 and 500 of the at least one pendant moieties.

Embodiment B18

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B17, wherein the surfactant-modified star macromolecule comprises a40:1 to 1:40 ratio of the at least one first polymeric arm to the atleast one second polymeric arm.

Embodiment B19

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B18, wherein the surfactant-modified star macromolecule comprises a4:1 ratio of the at least one first polymeric arm to the at least onsecond polymeric arm.

Embodiment B20

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B19, wherein L¹ is a covalent bond.

Embodiment B21

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B20, wherein G¹ is an ester moiety.

Embodiment B22

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B21, wherein G¹ is an amide moiety.

Embodiment B23

The surfactant-modified star macromolecule of Embodiments B21 or B22,wherein L¹ bonds to the carbonyl moiety of G¹.

Embodiment B24

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B23, wherein G¹ is a sulfonate moiety.

Embodiment B25

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B24, wherein G¹ is a sulfonamide moiety.

Embodiment B26

The surfactant-modified star macromolecule of Embodiments B24 or B25,wherein L¹ bonds to the sulfonyl moiety of G¹.

Embodiment B27

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B26, wherein L² is a covalent bond.

Embodiment B28

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B27, wherein L² comprises an aryl moiety, an ether moiety, a carbonylmoiety, or an unsaturated alkyl moiety.

Embodiment B29

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B28, wherein the surfactant-modified star macromolecule furthercomprises at least one third polymeric arm.

Embodiment B30

The surfactant-modified star macromolecule of Embodiment B29, whereinthe at least one third polymeric arm comprises a polymeric segmentcomprised of monomeric residues of polymerized hydrophilic monomer.

Embodiment B31

The surfactant-modified star macromolecule of Embodiment B30, whereinthe polymeric segment is a hydrophilic polymeric segment.

Embodiment B32

The surfactant-modified star macromolecule of any one of EmbodimentsB29-B31, wherein the at least one third polymeric arm comprises apolymeric segment comprised of monomeric residues of polymerizedhydrophobic monomer.

Embodiment B33

The surfactant-modified star macromolecule of Embodiment B32, whereinthe polymeric segment is a hydrophobic polymeric segment.

Embodiment B34

The surfactant-modified star macromolecule of any one of EmbodimentsB31-B33, wherein the hydrophilic polymeric segment of the at least onethird polymeric arm is proximal to the core.

Embodiment B35

The surfactant-modified star macromolecule of any one of EmbodimentsB31-B34, wherein the hydrophilic polymeric segment of the at least onethird polymeric arm is covalently attached to the core.

Embodiment B36

The surfactant-modified star macromolecule of any one of EmbodimentsB33-B35, wherein the hydrophobic polymeric segment is the distal segmentof the at least one third polymeric arm.

Embodiment B37

The surfactant-modified star macromolecule of any one of EmbodimentsB33-B36, wherein the at least one third polymeric arm consists of thehydrophilic polymeric segment and the hydrophobic polymeric segment.

Embodiment B38

The surfactant-modified star macromolecule of any one of EmbodimentsB33-B37, wherein a portion of the hydrophobic polymeric segment of theat least one third polymeric arm extends beyond the distal portion ofthe at least one first polymeric arm.

Embodiment B39

The surfactant-modified star macromolecule of any one of EmbodimentsB29-B38, wherein the surfactant-modified star macromolecule comprises aplurality of the at least one third polymeric arm.

Embodiment B40

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B39, wherein the further segment comprises one or more monomericresidues of polymerized hydrophobic monomers.

Embodiment B41

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B40, wherein the further segment comprises a plurality of monomericresidues of polymerized hydrophobic monomers.

Embodiment B42

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B41, wherein the further segment comprises one or more monomericresidues of polymerized hydrophilic monomers.

Embodiment B43

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B42, wherein the further segment comprises a plurality of monomericresidues of polymerized hydrophilic monomers.

Embodiment B44

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B43, wherein the hydrophilic polymeric segment of the at least onefirst polymeric arm is a homopolymeric segment, a copolymeric segment, ablock copolymeric segment, a blocky copolymeric segment, a gradientcopolymeric segment, or a random copolymeric segment.

Embodiment B45

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B44, wherein the hydrophilic polymeric segment of the at least onesecond polymeric arm is a homopolymeric segment, a copolymeric segment,a block copolymeric segment, a blocky copolymeric segment, a gradientcopolymeric segment, or a random copolymeric segment.

Embodiment B46

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B45, wherein the further segment is a polymeric segment.

Embodiment B47

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B46, wherein the further segment of the at least one second polymericarm is a homopolymeric segment, a copolymeric segment, a blockcopolymeric segment, a blocky copolymeric segment, a gradientcopolymeric segment, or a random copolymeric segment.

Embodiment B48

The surfactant-modified star macromolecule of any one of EmbodimentsB31-B47, wherein the hydrophilic polymeric segment of the at least onethird polymeric arm is a homopolymeric segment, a copolymeric segment, ablock copolymeric segment, a blocky copolymeric segment, a gradientcopolymeric segment, or a random copolymeric segment.

Embodiment B49

The surfactant-modified star macromolecule of any one of EmbodimentsB33-B48, wherein the hydrophobic polymeric segment of the at least onethird polymeric arm is a homopolymeric segment, a copolymeric segment, ablock copolymeric segment, a blocky copolymeric segment, a gradientcopolymeric segment, or a random copolymeric segment.

Embodiment B50

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B49, wherein the further segment is a surfactant-system thickeningpolymeric segment.

Embodiment B51

The surfactant-modified star macromolecule of any one of EmbodimentsB1-B50, wherein the surfactant-modified star macromolecule increases theviscosity of a surfactant-containing system.

Embodiment B52

The surfactant-modified star macromolecule of Embodiment B51, whereinthe surfactant-containing system is an aqueous system.

Embodiment B53

The macromolecule of any one of Embodiments B1-52, wherein thesurfactant is a nonionic surfactant, an anionic surfactant, anamphoteric surfactant, or a cationic surfactant.

Embodiment B54

The macromolecule of Embodiment B53, wherein the surfactant is anonionic surfactant.

Embodiment B55

The macromolecule of Embodiment B53, wherein the surfactant is a ananionic surfactant.

Embodiment B56

The macromolecule of Embodiment B53, wherein the surfactant is anamphoteric surfactant.

Embodiment B57

The macromolecule of Embodiment B53, wherein the surfactant is acationic surfactant.

Embodiment C1

A method of increasing the viscosity of a surfactant-containing aqueoussystem, comprising:

introducing a surfactant-system thickening macromolecule into thesurfactant-containing aqueous system, wherein the surfactant-systemthickening macromolecule comprises:

-   -   i) a core;    -   ii) at least one first polymeric arm, comprising a polymeric        segment comprised of monomeric residues of polymerized        hydrophilic monomers; and    -   iii) at least one second polymeric arm, comprises:        -   1) at least one pendant micelle-philic moiety; or        -   2) a polymeric segment comprised of at least one monomeric            residue of a polymerized micelle-philic monomer.

Embodiment C2

The method of Embodiment C1, wherein the core is a crosslinked polymericcore.

Embodiment C3

The method of Embodiments C1 or C2, wherein the core is a hydrophobiccrosslinked polymeric core.

Embodiment C4

The method of any one of Embodiments C1-C3, wherein the polymericsegment of the at least one first polymeric arm is comprised of between5 and 2000 monomeric residues of polymerized hydrophilic monomers.

Embodiment C5

The method of any one of Embodiments C1-C4, wherein the at least onesecond polymeric arm comprises the at least one pendant micelle-philicmoiety.

Embodiment C6

The method of any one of Embodiments C1-C5, wherein the at least onesecond polymeric arm comprises a plurality of the at least one pendantmicelle-philic moieties.

Embodiment C7

The method of any one of Embodiments C1-C6, wherein the at least onesecond polymeric arm comprises the polymeric segment comprised of the atleast one monomeric residue of polymerized micelle-philic monomer.

Embodiment C8

The method of any one of Embodiments C1-C7, wherein the polymericsegment of the at least one second polymeric arm comprised of the atleast one monomeric residue of polymerized micelle-philic monomer is amicelle-philic polymeric segment.

Embodiment C9

The method of any one of Embodiments C1-C8, wherein the polymericsegment of the at least one second polymeric arm is comprised of aplurality of the at least one monomeric residue of polymerizedmicelle-philic monomers.

Embodiment C10

The method of any one of Embodiments C1-C9, wherein the polymericsegment of the at least one second polymeric arm is comprised of between1 and 500 monomeric residues of polymerized micelle-philic monomers orpendant micelle-philic moieties.

Embodiment C11

The method of any one of Embodiments C1-C10, wherein a portion of the atleast one second polymeric arm comprising the at least one pendantmicelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer is further comprised of at least onemonomeric residue of a polymerized hydrophobic monomer.

Embodiment C12

The method of any one of Embodiments C1-C11, wherein a portion of the atleast one second polymeric arm comprising the at least one pendantmicelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer is further comprised of a pluralityof monomeric residues of a polymerized hydrophobic monomer.

Embodiment C13

The method of any one of Embodiments C1-C12, wherein a portion of the atleast one second polymeric arm comprising the at least one pendantmicelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer is further comprised of in the rangeof between 1 and 500 monomeric residues of a polymerized hydrophobicmonomer.

Embodiment C14

The method of any one of Embodiments C1-C13, wherein the at least onesecond polymeric arm further comprises a polymeric segment comprised ofmonomeric residues of polymerized hydrophilic monomers.

Embodiment C15

The method of any one of Embodiments C1-C14, wherein the polymericsegment of the at least one second polymeric arm comprised of themonomeric residues of polymerized hydrophilic monomers is a hydrophilicpolymeric segment.

Embodiment C16

The method of Embodiment C15, wherein the hydrophilic polymeric segmentof the at least one second polymeric arm is comprised of a plurality ofthe monomeric residues of polymerized hydrophilic monomers.

Embodiment C17

The method of Embodiments C15 or C16, wherein the hydrophilic polymericsegment of the at least one second polymeric arm is comprised of between10 and 5000 monomeric residues of the polymerized hydrophilic monomers.

Embodiment C18

The method of any one of Embodiments C1-C17, wherein the pendantmicelle-philic moieties or the monomeric residues of polymerizedmicelle-philic monomers are distal to the core.

Embodiment C19

The method of any one of Embodiments C15-C18, wherein at least a portionof the hydrophilic polymeric segment of the at least one secondpolymeric arm extends beyond the distal portion of the at least onefirst polymeric arm.

Embodiment C20

The method of any one of Embodiments C15-C19, wherein the hydrophilicpolymeric segment of said at least one second polymeric arm is proximalto the core.

Embodiment C21

The method of any one of Embodiments C1-C20, wherein the at least onefirst polymeric arm and the at least one second polymeric arm arecovalently attached to the core.

Embodiment C22

The method of any one of Embodiments C14-C21, wherein the at least onesecond polymeric arm comprises more of the monomeric residues ofpolymerized hydrophilic monomers than the pendant micelle-philicmoieties or the monomeric residues of polymerized micelle-philicmonomers.

Embodiment C23

The method of any one of Embodiments C14-C22, wherein the at least onesecond polymeric arm comprises in the range of between 2 and 1000 timesmore of the monomeric residues of polymerized hydrophilic monomers thanthe at least one pendant micelle-philic moiety or the at least onemonomeric residue of polymerized micelle-philic monomer.

Embodiment C24

The method of any one of Embodiments C14-C23, wherein the at least onesecond polymeric arm comprises 2 times, 3 times, 4 times, 5 times, 10times, 50 times, 100 times, or greater than 100 times, more of themonomeric residues of polymerized hydrophilic monomers than the at leastone pendant micelle-philic moiety or the at least one monomeric residuesof polymerized micelle-philic monomer.

Embodiment C25

The method of any one of Embodiments C1-C24, wherein the at least onesecond polymeric arm has a molecular weight of greater than 5,000 g/mol.

Embodiment C26

The method of any one of Embodiments C1-C25, wherein thesurfactant-system thickening macromolecule comprises a plurality of theat least one first polymeric arm.

Embodiment C27

The method of any one of Embodiments C1-C26, wherein thesurfactant-system thickening macromolecule comprises a plurality of theat least one second polymeric arm.

Embodiment C28

The method of any one of Embodiments C1-C27, wherein thesurfactant-system thickening macromolecule comprises a plurality of theat least one first polymeric arm and a plurality of the at least onesecond polymeric arm.

Embodiment C29

The method of any one of Embodiments C1-C28, wherein the ratio of the atleast one first polymeric arm to the at least one second polymeric armis in the range of between 40:1 and 1:40.

Embodiment C30

The method of any one of Embodiments C1-C29, wherein thesurfactant-system thickening macromolecule, optionally, furthercomprises at least one third polymeric arm, comprising a polymericsegment comprised of monomeric residues of polymerized hydrophobicmonomers, a polymeric segment comprised of monomeric residues ofpolymerized hydrophilic monomers, or both.

Embodiment C31

The method of Embodiment C30, wherein the surfactant-system thickeningmacromolecule further comprises the at least one third polymeric arm.

Embodiment C33

The method of Embodiments C30 or C31, wherein the at least one thirdpolymeric arm comprises a polymeric segment comprised of monomericresidues of polymerized hydrophilic monomers.

Embodiment C34

The method of any one of Embodiments C30-C33, wherein the polymericsegment of the at least one third polymeric arm comprised of themonomeric residues of polymerized hydrophilic monomers is a hydrophilicpolymeric segment.

Embodiment C35

The method of Embodiment C34, wherein the hydrophilic polymeric segmentof the at least one third polymeric arm is comprised of a plurality ofthe monomeric residues of polymerized hydrophilic monomers.

Embodiment C36

The method of Embodiments C34 or C35, wherein the hydrophilic polymericsegment of the at least one third polymeric arm is comprised of between1 and 500 monomeric residues of polymerized hydrophilic monomers.

Embodiment C37

The method of any one of Embodiments C30-C36, wherein the at least onethird polymeric arm comprises a polymeric segment comprised of monomericresidues of polymerized hydrophobic monomers.

Embodiment C38

The method of Embodiment C37, wherein the polymeric segment of the atleast one third polymeric arm comprised of the monomeric residues ofpolymerized hydrophobic monomers is a hydrophobic polymeric segment.

Embodiment C39

The method of Embodiments C37 or C38, wherein the hydrophobic polymericsegment of the at least one third polymeric arm is comprised of aplurality of the monomeric residues of polymerized hydrophobic monomers.

Embodiment C40

The method of any one of Embodiments C38-C39, wherein the hydrophobicpolymeric segment of the at least one third polymeric arm is comprisedof between 1 and 500 monomeric residues of polymerized hydrophobicmonomers.

Embodiment C41

The method of any one of Embodiments C34-C40, wherein the hydrophilicpolymeric segment of the at least one third polymeric arm is proximal tothe core.

Embodiment C42

The method of any one of Embodiments C34-C41, wherein the hydrophilicpolymeric segment of the at least one third polymeric arm is covalentlyattached to the core.

Embodiment C43

The method of any one of Embodiments C38-C42, wherein the hydrophobicpolymeric segment of the at least one third polymeric arm is distal tothe core.

Embodiment C44

The method of any one of Embodiments C38-C43, wherein a portion of thehydrophobic polymeric segment of the at least one third polymeric armextends beyond the distal portion of the at least one first polymericarm.

Embodiment C45

The method of any one of Embodiments C30-C44, wherein thesurfactant-system thickening macromolecule comprises a plurality of theat least third polymeric arm.

Embodiment C46

The method of any one of Embodiments C30-C45, wherein the at least onethird polymeric arm comprises more of the monomeric residues ofpolymerized hydrophilic monomers than the monomeric residues ofpolymerized hydrophobic monomers.

Embodiment C47

The method of any one of Embodiments C30-C46, wherein the at least onethird polymeric arm comprises in the range of between 2 and 1000 timesmore of the monomeric residues of polymerized hydrophilic monomers thanthe monomeric residues of polymerized hydrophobic monomers.

Embodiment C48

The method of any one of Embodiments C30-C47, wherein the at least onethird polymeric arm comprises 2 times, 3 times, 4 times, 5 times, 10times, 50 times, 100 times, or greater than 100 times, more of themonomeric residues of polymerized hydrophilic monomers than themonomeric residues of polymerized hydrophobic monomers.

Embodiment C49

The method of any one of Embodiments C30-C48, wherein the ratio of theat least one first polymeric arms to the at least one third polymericarms, the at least one third polymeric arms to the at least one secondpolymeric arms, and the at least one first polymeric arms to the sum ofthe at least one second polymeric arms and the at least one thirdpolymeric arms, are independently in the range of between 40:1 and 1:40.

Embodiment C50

The method of any one of Embodiments C1-C49, wherein thesurfactant-system thickening macromolecule is represented by Formula C:

[(P1)_(q1)]_(r)-Core-[(P3)_(q3)-(P2)_(q2)],  Formula C

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents the hydrophilic polymeric segment of        the at least one first polymeric arm comprised of monomeric        residues of polymerized hydrophilic monomers;    -   P2 independently represents the polymeric segment of the at        least one second polymeric arm comprised of:        -   1) a polymerized backbone comprising at least one pendant            micelle-philic moiety, or        -   2) at least one monomeric residue of a polymerized            micelle-philic monomer,    -   P3 independently represents the hydrophilic polymeric segment of        the at least one second polymeric arm comprised of monomeric        residues of polymerized hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   r independently represents the number of the at least one first        polymeric arms covalently attached to the Core; and    -   s independently represents the number of the at least one second        polymeric arms covalently attached to the Core.

Embodiment C51

The method of Embodiment C50, wherein the ratio of r:s is in the rangeof between 40:1 and 1:40.

Embodiment C52

The method of Embodiments C50 or C51, wherein the ratio of r:s is 4:1.

Embodiment C53

The method of any one of Embodiments C1-C52, wherein thesurfactant-system thickening macromolecule is represented by Formula D:

wherein:

-   -   Core represents a crosslinked polymeric segment;    -   P1 independently represents the hydrophilic polymeric segment of        the at least one first polymeric arm comprised of monomeric        residues of polymerized hydrophilic monomers;    -   P2 independently represents the polymeric segment of the at        least one second polymeric arm comprised of:        -   1) a polymerized backbone comprising at least one pendant            micelle-philic moiety, or        -   2) at least one monomeric residue of a polymerized            micelle-philic monomer,    -   P3 independently represents the hydrophilic polymeric segment of        the at least one second polymeric arm comprised of monomeric        residues of polymerized hydrophilic monomers;    -   P4 independently represents the hydrophobic polymeric segment of        the at least one third polymeric arm comprised of monomeric        residues of polymerized hydrophobic monomers;    -   P5 independently represents the hydrophilic polymeric segment of        the at least one third polymeric arm comprised of monomeric        residues of polymerized hydrophilic monomers;    -   q1 independently represents the number of monomeric residues in        P1;    -   q2 independently represents the number of monomeric residues in        P2;    -   q3 independently represents the number of monomeric residues in        P3;    -   q4 independently represents the number of monomeric residues in        P4;    -   q5 independently represents the number of monomeric residues in        P5;    -   r independently represents the number of the at least one first        polymeric arms covalently attached to the Core;    -   s independently represents the number of the at least one second        polymeric arms covalently attached to the Core; and    -   t independently represents the number of the at least one third        polymeric arms covalently attached to the Core.

Embodiment C54

The method of Embodiment C53, wherein the ratio of r:s, and, if t is notzero, the ratio of r:t, t:s, and r:(s+t), are independently in the rangeof between 40:1 and 1:40.

Embodiment C55

The method of Embodiments C53 or C54, wherein the ratio of r:s is 4:1.

Embodiment C56

The method of any one of Embodiments C50-C55, wherein q1 has a valuebetween 5 and 2000.

Embodiment C57

The method of any one of Embodiments C50-C56, wherein q2 has a valuebetween 1 and 500.

Embodiment C58

The method of any one of Embodiments C50-C57, wherein q3 has a valuebetween 10 and 5000.

Embodiment C59

The method of any one of Embodiments C53-C58, wherein q4 has a valuebetween 1 and 500.

Embodiment C60

The method of any one of Embodiments C53-C59, wherein q5 has a valuebetween 10 and 5000.

Embodiment C61

The method of any one of Embodiments C50-C60, wherein r has a value inthe range of from 1 to 1000.

Embodiment C62

The method of any one of Embodiments C50-C61, wherein s has a value inthe range of from 1 to 1000.

Embodiment C63

The method of any one of Embodiments C53-C62, wherein t has a value inthe range of from 0 to 1000.

Embodiment C64

The method of any one of Embodiments C50-C63, wherein q3 is greater thanq2.

Embodiment C65

The method of any one of Embodiments C50-C64, wherein q3 is in the rangeof between 2 and 1000 times greater than q2.

Embodiment C66

The method of any one of Embodiments C50-C65, wherein q3 is 2 times, 3times, 4 times, 5 times, 10 times, 50 times, 100 times, or greater than100 times, greater than q2.

Embodiment C67

The method of any one of Embodiments C53-C66, wherein q5 is greater thanq4.

Embodiment C68

The method of any one of Embodiments C53-C67, wherein q5 is in the rangeof between 2 and 1000 times greater than q4.

Embodiment C69

The method of any one of Embodiments C53-C68, wherein q5 is 2 times, 3times, 4 times, 5 times, 10 times, 50 times, 100 times, or greater than100 times, greater than q4.

Embodiment C70

The method of any one of Embodiments C50-C69, wherein P2 comprises theat least one pendant micelle-philic moiety.

Embodiment C71

The method of any one of Embodiments C50-C70, wherein P2 comprises aplurality of the at least one pendant micelle-philic moiety.

Embodiment C72

The method of any one of Embodiments C1-C71, wherein each of the atleast second polymeric arms comprise in the range of between 1 and 500pendant micelle-philic moieties.

Embodiment C73

The method of any one of Embodiments C1-C72, wherein the at least onependant micelle-philic moiety is represented by the formula:

[L¹-G¹-L²-G²]

wherein:

-   -   G¹ independently represents a residue of a hydrophilic moiety of        the surfactant;    -   G² independently represents a residue of a hydrophobic moiety of        the surfactant;    -   L¹ independently represents a linking group or a covalent bond,        attaching G¹ to the at least one second polymeric arm; and    -   L² independently represents a linking group or a covalent bond,        linking G¹ and G².

Embodiment C74

The method of Embodiment C73, wherein G² comprises a C₆ or greater alkylmoiety, a fluorine-modified C₄ or greater alkyl moiety, or a C₆ orgreater alkenyl moiety.

Embodiment C75

The method of Embodiments C73 or C74, wherein G² comprises a C₁₃ orgreater saturated fatty alkyl moiety, a C₁₂ or greater mono-unsaturatedfatty alkyl moiety, or a C₁₂ or greater poly-unsaturated fatty alkylmoiety.

Embodiment C76

The method of any one of Embodiments C73-C75, wherein G² comprises a C₁₄or greater saturated fatty alkyl moiety.

Embodiment C77

The method of any one of Embodiments C73-C76, wherein G² comprises a C₁₆or greater saturated fatty alkyl moiety.

Embodiment C78

The method of any one of Embodiments C73-C77, wherein G² comprises a C₁₈or greater saturated fatty alkyl moiety.

Embodiment C79

The method of any one of Embodiments C73-C78, wherein L¹ is a covalentbond, G¹ is an ester moiety, and G² comprises a C₁₈ or greater saturatedfatty alkyl moiety.

Embodiment C80

The method of any one of Embodiments C73-C79, wherein G² comprises thehydrophobic moiety of a commercially suitable surfactant and/orregistered in TSCA.

Embodiment C81

The method of any one of Embodiments C73-C80, wherein G² comprises a C₁₉or greater saturated fatty alkyl moiety.

Embodiment C82

The method of any one of Embodiments C73-C81, wherein the G² furthercomprises an aryl moiety, an ether moiety, a carbonyl moiety, or anunsaturated alkyl moiety.

Embodiment C83

The method of any one of Embodiments C73-C82, wherein L¹ is a covalentbond.

Embodiment C84

The method of any one of Embodiments C73-C83, wherein G¹ is an estermoiety.

Embodiment C85

The method of any one of Embodiments C73-C84, wherein G¹ is an amidemoiety.

Embodiment C86

The method of Embodiments C84 or C85, wherein L¹ bonds to the carbonylmoiety of G¹.

Embodiment C87

The method of any one of Embodiments C73-C86, wherein G¹ is a sulfonatemoiety.

Embodiment C88

The method of any one of Embodiments C73-C87, wherein G¹ is asulfonamide moiety.

Embodiment C89

The method of Embodiments C87 or C88, wherein L¹ bonds to the sulfonylmoiety of G¹.

Embodiment C90

The method of any one of Embodiments C73-C89, wherein L² is a covalentbond.

Embodiment C91

The method of any one of Embodiments C73-C90, wherein L² comprises anaryl moiety, an ether moiety, a carbonyl moiety, or an unsaturated alkylmoiety.

Embodiment C92

The method of any one of Embodiments C1-C91, wherein a portion of the atleast one second polymeric arm is represented by Formula E:

wherein:

-   -   R¹¹, R¹², R¹³ independently represent hydrogen, methyl, ethyl,        or C₃₋₁₈ alkyl, for example C₃₋₆ alkyl, C₆₋₁₂ alkyl, or C₁₂₋₁₈        alkyl; wherein the alkyl may be branched or unbranched, linear        or cyclic, and may be optionally substituted with one or more        halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol);    -   R¹⁴ independently represents C₁₋₁₂ hydrocarbyl, —C₁₋₁₂        hydrocarbyl-(O—C₁₋₆ hydrocarbyl)_(w), —C₁₋₁₂        hydrocarbyl-((CO)O—C₁₋₆ hydrocarbyl)_(w), —C₁₋₁₂        hydrocarbyl-((CO)NH—C₁₋₆ hydrocarbyl)_(w); wherein each        hydrocarbyl portion independently may be branched or unbranched,        linear or cyclic, saturated (alkyl) or unsaturated (alkenyl),        and may be optionally substituted with one or more halogens,        C₁₋₆ alkoxy groups, or poly(ethylene glycol);    -   R¹⁵ independently represents C₁₃₋₄₀ hydrocarbyl, —C₁₃₋₄₀        hydrocarbyl-(O—C₁₋₆ hydrocarbyl)_(w), —C₁₃₋₄₀        hydrocarbyl-((CO)O-Cis hydrocarbyl)_(w), C₁₃₋₄₀        hydrocarbyl-((CO)NH—C₁₋₆ alkyl)_(w); wherein each hydrocarbyl        portion independently may be branched or unbranched, linear or        cyclic, saturated (alkyl) or unsaturated (alkenyl), and may be        optionally substituted with one or more halogens, C₁₋₆ alkoxy        groups, or poly(ethylene glycol); or a hydrophobic moiety of a        surfactant, a hydrophobic moiety of a lipid, or a hydrophobic        moiety of a fatty alcohol;    -   Y represents a covalent bond, ethylene glycol, poly(ethylene        glycol), polyether, polyamide, C₁₋₆ alkyl, or combinations        thereof, or is independently absent;    -   m independently represents a value in the range of 1-500;    -   n independently represents a value in the range of 1-500; and    -   w independently represents a value in the range of 1-1000.

Embodiment C93

The method of Embodiment C92, wherein the portion of the at least onesecond polymeric arm represented by Formula E is a copolymeric segment,a block copolymeric segment, a blocky copolymeric segment, a gradientcopolymeric segment, or a random copolymeric segment.

Embodiment C94

The method of any one of Embodiments C50-C93, wherein P2 comprises theat least one monomeric residue of a polymerized micelle-philic monomer.

Embodiment C95

The method of any one of Embodiments C50-C94, wherein P2 comprises aplurality of the at least one monomeric residue of a polymerizedmicelle-philic monomer.

Embodiment C96

The method of any one of Embodiments C1-C95, wherein the portion of theat least one second polymeric arm comprising the at least one monomericresidue of a polymerized micelle-philic monomer is a micelle-philicpolymeric segment.

Embodiment C97

The method of Embodiment C96, wherein the micelle-philic polymericsegment is further comprised of at least one monomeric residue of apolymerized hydrophobic monomer.

Embodiment C98

The method of Embodiment C96, wherein the micelle-philic polymericsegment is further comprised of a plurality of monomeric residues of apolymerized hydrophobic monomer.

Embodiment C99

The method of any one of Embodiments C50-C98, wherein P2 is furthercomprised of at least one monomeric residue of a polymerized hydrophobicmonomer.

Embodiment C100

The method of any one of Embodiments C50-C99, wherein P2 is furthercomprised of a plurality of monomeric residues of a polymerizedhydrophobic monomer.

Embodiment C101

The method of any one of Embodiments C96-C100, wherein themicelle-philic polymeric segment is further comprised of at least onemonomeric residue of a polymerized hydrophilic monomer.

Embodiment C102

The method of any one of Embodiments C96-C100, wherein themicelle-philic polymeric segment is further comprised of a plurality ofmonomeric residues of a polymerized hydrophilic monomer.

Embodiment C103

The method of any one of Embodiments C50-C102, wherein P2 is furthercomprised of at least one monomeric residue of a polymerized hydrophilicmonomer.

Embodiment C104

The method of any one of Embodiments C50-C102, wherein P2 is furthercomprised of a plurality of monomeric residues of a polymerizedhydrophilic monomer.

Embodiment C105

The method of any one of Embodiments C1-C104, wherein each of the atleast second polymeric arms comprise in the range of between 1 and 500monomeric residues of a polymerized micelle-philic monomer.

Embodiment C106

The method of any one of Embodiments C1-C105, wherein the at least onesecond polymeric arm comprises the at least one pendant micelle-philicmoiety and the at least one monomeric residue of a polymerizedmicelle-philic monomer.

Embodiment C107

The method of any one of Embodiments C1-C106, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises a C₆ or greater alkylmoiety, a fluorine-modified C₄ or greater alkyl moiety, or a C₆ orgreater alkenyl moiety.

Embodiment C108

The method of any one of Embodiments C1-C107, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises a C₁₃ or greater saturatedfatty alkyl moiety, a C₁₂ or greater mono-unsaturated fatty alkylmoiety, or a C₁₂ or greater poly-unsaturated fatty alkyl moiety.

Embodiment C109

The method of any one of Embodiments C1-C108, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises a C₁₃ or greater pendantmoiety.

Embodiment C110

The method of any one of Embodiments C1-C109, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises a C₁₃-C₄₀ pendant moiety.

Embodiment C111

The method of any one of Embodiments C1-C110, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises a C₁₃-C₃₀ pendant moiety.

Embodiment C112

The method of any one of Embodiments C1-C111, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises a C₁₃-C₂₀ pendant moiety.

Embodiment C113

The method of any one of Embodiments C1-C112, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises a C₁₄ or greater saturatedfatty alkyl moiety.

Embodiment C114

The method of any one of Embodiments C1-C113, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises a C₁₆ or greater saturatedfatty alkyl moiety.

Embodiment C115

The method of any one of Embodiments C1-C114, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises a C₁₈ or greater saturatedfatty alkyl moiety.

Embodiment C116

The method of any one of Embodiments C1-C115, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises a C₁₉ or greater saturatedfatty alkyl moiety.

Embodiment C117

The method of any one of Embodiments C1-C116, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises a C₁₉-C₄₀ pendant moiety.

Embodiment C118

The method of any one of Embodiments C1-C117, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises the hydrophobic moiety of acommercially suitable surfactant and/or registered in TSCA.

Embodiment C119

The method of any one of Embodiments C1-C118, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer further comprises an aryl moiety, anether moiety, a carbonyl moiety, or an unsaturated alkyl moiety.

Embodiment C120

The method of any one of Embodiments C1-C119, wherein the micelle-philicmonomer comprises C₆₋₄₀ alkyl acrylate; C₆₋₄₀ alkyl alkyl acrylate;C₆₋₄₀ alkyl acrylamide; C₆₋₄₀ alkyl alkyl acrylamide; C₆₋₄₀ alkyl vinylether, or C₆₋₄₀ alkyl allyl ether.

Embodiment C121

The method of any one of Embodiments C1-C120, wherein the micelle-philicmonomer comprises C₁₃ or greater alkyl acrylate; C₁₁ or greater alkylalkyl acrylate; C₁₉ or greater alkyl acrylamide; C₁₃ or greater alkylalkyl acrylamide; C₂ or greater alkyl vinyl ether; or C1 or greateralkyl allyl ether.

Embodiment C122

The method of any one of Embodiments C1-C121, wherein the micelle-philicmonomer comprises C₁₃₋₄₀ alkyl acrylate; C₁₁₋₄₀ alkyl alkyl acrylate;C₁₉₋₄₀ alkyl acrylamide; C₁₃₋₄₀ alkyl alkyl acrylamide; C₂₋₄₀ alkylvinyl ether, or C₁₋₄₀ alkyl allyl ether.

Embodiment C123

The method of any one of Embodiments C108-C122, wherein the saturatedfatty alkyl pendant moiety is: tridecyl, isotridecyl, myristyl,pentadecyl, cetyl, palmityl, heptadecyl, stearyl, nonadecyl, arachidyl,heneicosyl, behenyl, lignoceryl, ceryl (heptacosanyl), montanyl,nonacosanyl, myricyl, dotriacontanyl, geddyl, or cetostearyl pendantmoiety.

Embodiment C124

The method of Embodiment C123, wherein the saturated fatty alkyl pendantmoiety is a stearyl pendant moiety.

Embodiment C125

The method of any one of Embodiments C1-C124, wherein the at least onependant micelle-philic moiety or the at least one monomeric residue of apolymerized micelle-philic monomer comprises an unsaturated fatty alkylpendant moiety.

Embodiment C126

The method of Embodiment C125, wherein the unsaturated fatty alkylpendant moiety is mono-unsaturated or poly-unsaturated.

Embodiment C127

The method of Embodiment C126, wherein the poly-unsaturated fatty alkylpendant moiety is a di-, tri, tetra, penta, or hexa-unsaturated fattyalkyl pendant moiety.

Embodiment C128

The method of any one of Embodiments C1-C127, wherein the micelle-philicmonomer comprises C₁₃ or greater alkenyl acrylate; C₁ or greater alkenylalkyl acrylate; C₁₉ or greater alkenyl acrylamide; C₁₃ or greateralkenyl alkyl acrylamide; C₂ or greater alkenyl vinyl ether, or C₁ orgreater alkenyl allyl ether.

Embodiment C129

The method of any one of Embodiments C1-C128, wherein the micelle-philicmonomer comprises C₁₃₋₄₀ alkenyl acrylate; C₁₁₋₄₀ alkenyl alkylacrylate; C₁₉₋₄₀ alkenyl acrylamide; C₁₃₋₄₀ alkenyl alkyl acrylamide;C₂₋₄₀ alkenyl vinyl ether, or C₁₋₄₀ alkenyl allyl ether.

Embodiment C130

The method of Embodiments C128 or C129, wherein the alkenyl group is amono-, di-, tri, tetra, penta, or hexa-alkenyl group.

Embodiment C131

The method of any one of Embodiments C125-C130, wherein the unsaturatedfatty alkyl pendant moiety is: myristoleyl, palmitoleyl, sapienyl,oleyl, elaidyl, vaccenyl, linoleyl, linoelaidyl, α-linolenyl,arachidonyl, eicosapentaenoyl, erucyl, or docosahexaenoyl pendantmoiety.

Embodiment C132

The method of any one of Embodiments C1-C131, wherein the micelle-philicmonomer is represented by Formula I-V:

wherein:

-   -   R¹, R², and R³ independently represent hydrogen, methyl, ethyl,        or C₃₋₁₈ alkyl, for example C₃₋₆ alkyl, C₆₋₁₂ alkyl, or C₁₂₋₁₈        alkyl; wherein the alkyl may be branched or unbranched, linear        or cyclic, and may be optionally substituted with one or more        halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol);    -   R⁴ and R⁷ independently represent C₁₃ or greater alkyl, —C₆ or        greater alkyl-(O—C₁₋₆ alkyl)_(n), C₆ or greater alkenyl, or C₆        or greater alkenyl-(O—C₁₋₆ alkyl)_(n); or when R³ is C₁ or        greater, then R⁴ may independently represent C₁₁ or greater        alkyl, —C₆ or greater alkyl —(O—C₁₋₆ alkyl)_(n), C₆ or greater        alkenyl, or C₆ or greater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein        each alkyl portion independently may be branched or unbranched,        linear or cyclic, saturated or unsaturated, and may be        optionally substituted with one or more halogens, C₁₋₆ alkoxy        groups, or poly(ethylene glycol);    -   R⁵ independently represents C₁₉ or greater alkyl, —C₆ or greater        alkyl —(O—C₁₋₆ alkyl)_(n), C₆ or greater alkenyl, or C₆ or        greater alkenyl-(O—C₁₋₆ alkyl)_(n); or when R⁶ is C₁ or greater,        then R⁵ may independently represent C₁₃ or greater alkyl, —C₆ or        greater alkyl —(O—C₁₋₆ alkyl)_(n), C₆ or greater alkenyl, or C₆        or greater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkyl        portion independently may be branched or unbranched, linear or        cyclic, saturated or unsaturated, and may be optionally        substituted with one or more halogens, C₁₋₆ alkoxy groups, or        poly(ethylene glycol);    -   R⁶ independently represents hydrogen, C₁₋₁₈ alkyl, —C₁₋₁₈        alkyl-(O—C₁₋₆ alkyl)_(n), or is R⁴, or is R⁵; wherein each alkyl        portion independently may be branched or unbranched, linear or        cyclic, saturated or unsaturated, and may be optionally        substituted with one or more halogens, C₁₋₆ alkoxy groups, or        poly(ethylene glycol);    -   R⁸ independently represents C₂ or greater alkyl, —C₂ or greater        alkyl-(O—C₁₋₆ alkyl)_(n), C₃ or greater alkenyl, —C₃ or greater        alkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkyl portion        independently may be branched or unbranched, linear or cyclic,        saturated or unsaturated, and may be optionally substituted with        one or more halogens, C₁₋₆ alkoxy groups, or poly(ethylene        glycol);    -   R⁹ independently represents C₁ or greater alkyl, —C₁ or greater        alkyl-(O—C₁₋₆ alkyl)_(n), C₃ or greater alkenyl, —C₃ or greater        alkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkyl portion        independently may be branched or unbranched, linear or cyclic,        saturated or unsaturated, and may be optionally substituted with        one or more halogens, C₁₋₆ alkoxy groups, or poly(ethylene        glycol); or    -   R⁴, R⁵, R⁷, R⁸, R⁹ independently represent a hydrophobic portion        of a surfactant, a hydrophobic portion of a lipid, or a        hydrophobic portion of a fatty alcohol;    -   A¹, A², A³ and A⁴ independently represent CH, CR¹⁰, or N,        wherein at least two of A¹, A², A³ and A⁴ is CH or CR¹⁰;    -   R¹⁰ independently represents hydrogen, C₁₋₁₀ alkyl, halogen,        hydroxyl, C₁₋₁₀ alkoxy; wherein the alkyl or alkoxy may be        branched or unbranched, linear or cyclic, and may be optionally        substituted with one or more halogens, C₁₋₆ alkoxy groups, or        poly(ethylene glycol);    -   Y independently represents a covalent bond, —O—, —S—, —N(H)—,        —N(R¹)—, —(CO)—, —S(O)—, —S(O)₂—, —S(O)₂N(R¹)—, —(CO)N(R¹)—,        —N(R¹)—(CO)—, —(CO)O—, or —O—(CO)—;    -   L¹ independently represents a covalent bond, ethylene glycol,        poly(ethylene glycol), polyether, polyamide, C₁₋₆ alkyl,        —(CO)N(R¹)—, —N(R¹)—(CO)—, —(CO)O—, —O—(CO)—, or combinations        thereof, or is independently absent; or    -   L¹ independently represents a hydrophilic portion of a        surfactant, a hydrophilic portion of a lipid, or a hydrophilic        portion of a fatty alcohol;    -   L² independently represents (CH₂)₁₋₄₀, C₁₋₄₀ alkyl, (O—C₂₋₆        alkyl)_(n), or (C₂₋₆ alkyl)-(O—C₂₋₆ alkyl)_(n); wherein the        alkyl may be branched or unbranched, linear or cyclic, and may        be optionally substituted with one or more halogens, C₁₋₆ alkoxy        groups, or poly(ethylene glycol); and    -   n independently represents a value in the range of 1-1000.

Embodiment C133

The method of any one of Embodiments C50-C132, wherein the polymericsegment P1, P2, or P3 is a homopolymeric segment, a copolymeric segment,a block copolymeric segment, a blocky copolymeric segment, a gradientcopolymeric segment, or a random copolymeric segment.

Embodiment C134

The method of any one of Embodiments C53-C133, wherein the polymericsegment P4 or P5 is a homopolymeric segment, a copolymeric segment, ablock copolymeric segment, a blocky copolymeric segment, a gradientcopolymeric segment, or a random copolymeric segment.

Embodiment C135

The method of any one of Embodiments C1-C134, wherein thesurfactant-system thickening macromolecule has a molecular weight (Mn)in the range of between 5,000 g/mol and 10,000,000 g/mol.

Embodiment C136

The method of any one of Embodiments C1-C135, wherein thesurfactant-system thickening macromolecule has a molecular weight (Mn)of greater than 100,000 g/mol.

Embodiment C137

The method of any one of Embodiments C1-C136, wherein thesurfactant-system thickening macromolecule has a molecular weight (Mn)in the range of between 100,000 g/mol and 2,000,000 g/mol.

Embodiment C138

The method of any one of Embodiments C1-C137, wherein the molecularweight (Mn) of the at least one polymeric arm is between 1,000 g/mol to250,000 g/mol.

Embodiment C139

The method of any one of Embodiments C1-C138, wherein the molecularweight (Mn) of the at least one polymeric arm is between 10,000 g/moland 200,000 g/mol.

Embodiment C140

The method of any one of Embodiments C1-C139, wherein thesurfactant-system thickening macromolecule is a water soluble mikto starmacromolecule.

Embodiment C141

The macromolecule of any one of Embodiments C1-C140, wherein thesurfactant is a nonionic surfactant, an anionic surfactant, anamphoteric surfactant, or a cationic surfactant.

Embodiment C142

The macromolecule of Embodiment C141, wherein the surfactant is anonionic surfactant.

Embodiment C143

The macromolecule of Embodiment C141, wherein the surfactant is a ananionic surfactant.

Embodiment C144

The macromolecule of Embodiment C141, wherein the surfactant is anamphoteric surfactant.

Embodiment C145

The macromolecule of Embodiment C141, wherein the surfactant is acationic surfactant.

Embodiment D1

A method of increasing the viscosity of a surfactant-containing aqueoussystem, comprising: introducing the surfactant-system thickeningmacromolecule of any one of Embodiments A1-A160 into thesurfactant-containing aqueous system.

Embodiment D2

A method of increasing the viscosity of a surfactant-containing aqueoussystem, comprising: introducing the surfactant-modified starmacromolecule of any one of Embodiments B1-B57 into thesurfactant-containing aqueous system.

EXAMPLES

TABLE 1 Abbreviation Name Form Purity Commercial Source St styreneliquid 99% Sigma Aldrich MMA methyl methacrylate liquid 99% SigmaAldrich tBA tert-butyl acrylate liquid 98% Sigma Aldrich tBMA tert-butylmethacrylate liquid 98% Sigma Aldrich AA acrylic acid (formed bydeprotection) NA NA NA Me6TREN tris[2-(dimethylamino)ethyl]amine liquid95% ATRP Solutions TPMA tris(2-pyridylmethyl)amine solid 95% ATRPSolutions Sn(EH)₂ tin(II) 2-ethylhexanoate liquid 95% Sigma Aldrich DVBdivinylbenzene liquid 80% Sigma Aldrich FA formic acid liquid 99% SigmaAldrich THF tetrahydrofuran liquid 99.9%   Sigma Aldrich NaOH sodiumhydroxide solid 98% Sigma Aldrich EBiB ethyl α-bromoisobutyrate liquid98% Sigma Aldrich DEBMM diethyl 2- bromo-2-methylmalonate liquid 98%Sigma Aldrich DMF diethylformamide liquid 98% Sigma Aldrich anisoleliquid 99% Sigma Aldrich MeCN acetonitrile liquid 99.8%   Sigma AldrichNaCl sodium chloride solid 99.7%   Fisher Chemical V-702,2′-azobis(4-methoxy-2,4-dimethyl solid 99% Wako valeronitrile) HClhydrochloric acid liquid 37% Sigma Aldrich SMA Stearyl methacrylateSolid 80% Sigma Aldrich SLES Sodium lauryl ether sulfate liquid 25.5%active   BASF CB Cocamidopropyl Betaine liquid 30% active Croda CHCocamidopropyl hydroxysultaine liquid 50% active Croda

Equipment:

The viscosity measurements reported in the examples detailed below weredetermined utilizing a BROOKFIELD® LVDV-E Viscometer, which utilized oneof the following spindles:

LVDVE SC4-31—providing a shear rate (sec⁻¹) of 0.34 N per rpm; can beused in samples having a viscosity range of 30-100K cP;

LVDVE SC4-34—providing a shear rate (sec⁻¹) of 0.28 N per rpm; can beused in samples having a viscosity range of 60-200K cP; and

LVDVE SC4-25—providing a shear rate (sec⁻¹) of 0.22 N per rpm; can beused in samples having a viscosity range of 800-1.6M cP.

Synthesis of Star Copolymers (Example 1-4) Example 1: Synthesis of[((MMA)₂₀-co-(SMA)₇)-b-(AA)₃₅₁]/[(AA)₆₄] Star

A “one-pot” procedure was used for the preparation of a poly(acrylicacid) based miktoarm star macromolecule similar to that described inScheme 1. The miktoarm star macromolecule with[((MMA)₂₀-co-(SMA)₇)-b-(AA)₃₅₁] and [(AA)₆₄] arms (molar ratio of arms:1/4) was prepared as follows.

Step 1: Synthesis of a Poly(methyl methacrylate)-co-Poly(stearylmethacrylate) Macroinitiator [(MMA)₂₀-co-(SMA)₇]

Macroinitiator [(MMA)₂₀-co-(SMA)₇] was synthesized by using ActivatorsReGenerated by Electron Transfer (ARGET) ATRP. The molar ratio ofreagents used was:MMA/SMA/DEBMM/CuBr₂/TPMA/Sn(EH)₂=40/10/1/0.005/0.0175/0.05 in anisole(20% v/v). In a 250 mL round bottom flask, MMA (48 mL), SMA (38 g), andDEBMM (2.14 mL), were added to anisole (12 mL). A pre-mixed solution ofCuBr₂/TPMA (13.3 mg CuBr2/57 mg TPMA) in DMF (1.5 mL) was added to theflask, which was then sealed with a rubber septum, and purged withnitrogen for 1.0 hour. The flask was then placed in a 75° C. oil bath,and injected with Sn(EH)₂ (0.193 mL) to start the reaction. Samples weretaken to monitor the monomer conversion. After 23 hours, the flask wasopened to air and the reaction was stopped. The polymer was purified byprecipitation into methanol. The molecular weight measured by GPC was4461 g/mol and PDI was 1.12. Yield: 22 grams of polymer was obtainedafter purification.

Steps 2-4: Synthesis of [((MMA)₂₀-Co-(SMA)₇)-b-(tBA)₃₅₁]/[(tBA)₆₄] Arms,Crosslinking and Deprotection to Produce[((MMA)₂₀-Co-(SMA)₇)-b-(AA)₃₅₁]/[(AA)₆₄] Star Copolymer in “One Pot”

The synthesis includes 3 steps: the synthesis of arms, the cross-linkingof arms and the deprotection of star polymers. For the synthesis ofarms, the molar ratio of reagents is: tBA/[(MMA)₂₀-co-(SMA)₇] (fromExample 1, Step 1)/EBiB/CuBr₂/Me₆TREN/V-70=160/0.2/0.8/0.01/0.05/0.025.Anisole (33%, v/v) was used as solvent. The synthesis of arms wasconducted as follows. In a 22 mL vial, CuBr₂ (19.05 mg) was dissolved inDMF (6.6 mL) with Me₆TREN (0.1 mL) to make a stock solution. A 250 mLround bottom flask was charged with [(MMA)₂₀-co-(SMA)₇] (1.52 g) fromstep 1, tBA (40 mL), and anisole (20 mL). The DMF solution ofCuBr₂/Me₆TREN (1.32 mL) was added, and the resulting polymer solutionwas stirred for 10 min in order to dissolve the macroinitiator. Theflask was sealed with a rubber septum and the solution was purged withnitrogen for 40 minutes. In a 22 mL vial, V-70 (13.2 mg) was dissolvedin acetone (1 mL) and purged with N₂, and the resulting solution wastransferred into 1 mL syringe under N₂. The reaction flask was heated upto 65° C., and the reaction was injected with 0.1 mL of the V-70/acetonesolution every 20 minutes. Sample was taken for analysis and as theconversion of monomer reached 44%, 0.2 mL of EBiB was injected. Afterthat, 0.1 mL of the V-70/acetone solution was injected every 30 minutes.As the monomer conversion reached 85%, the reaction flask was open toair. The cross-linking of arms was continued in the same flask with themolar ratio of reagents as: [((MMA)₂₀-co-(SMA)₇)-b-(tBA)₃₅₁]/[(tBA)₆₄]arms/DVB/CuBr₂/TPMA/Sn(EH)₂=1/25/0.02/0.2/0.2 in anisole. A solution ofCuBr₂/TPMA (3.74 mg CuBr₂/30 mg TPMA) in DMF (2.0 mL), DVB (4.28 mL),and anisole (28 mL) were added to the reaction flask, and the resultingpolymer solution was purged with N₂ for 1 h, and then heated up to 95°C. To the reaction flask was injected Sn(EH)₂ (0.08 mL), to start thereaction. Sample was taken for analysis and 16 hours later as theconversion of DVB reached 77%, the heating was stopped and the flask wasopened to air. Molecular weight of[((MMA)₂₀-co-(SMA)₇)-b-(tBA)₃₅₁]/[(tBA)₆₄] star molecule was determinedby GPC. Mn=78817 g/mol, Mp=205801 g/mol, PDI=2.47. The GPC results werepresent in FIG. 1. The deprotection was then conducted by adding formicacid (20 mL) and sulfuric acid (0.1 mL) to the reaction flask. Thereaction mixture was heated up to 75° C. After 6 hours, the reaction wasfinished. The liquid was decanted and the solid polymer was washed withacetonitrile and acetone in the flask for 3 times. The solid polymer wasrecovered from the flask and dried in vacuum oven at 40° C. for 1 day.Yield: the mass of [((MMA)₂₀-co-(SMA)₇)-b-(AA)₃₅₁]/[(AA)₆₄] star was 18gram.

Example 2: Synthesis of [((MMA)₂₀-Co-(SMA)₇)-b-(AA)₁₆₉]/[(AA)₆₆] Star

The “one-pot” procedure was used for the preparation of a poly(acrylicacid) based miktoarm star macromolecule similar to that described inScheme 1. The miktoarm star macromolecule with[((MMA)₂₀-co-(SMA)₇)-b-(AA)₁₆₉] and [(AA)₆₆] arms (molar ratio of arms:1/4) was prepared as follows.

Step 1: Synthesis of a Poly(methyl methacrylate)-co-Poly(stearylmethacrylate) Macroinitiator [(MMA)₂₀-co-(SMA)₇]

Macroinitiator [(MMA)₂₀-co-(SMA)₇] was synthesized as described inExample 1, Step 1.

Steps 2-4: Synthesis of [((MMA)₂₀-Co-(SMA)₇)-b-(tBA)₁₆₉]/[(tBA)₆₆] Arms,Crosslinking and Deprotection to Produce[((MMA)₂₀-Co-(SMA)₇)-b-(AA)₁₆₉]/[(AA)₆₆] Star Copolymer in “One Pot”

The synthesis includes 3 steps: the synthesis of arms, the cross-linkingof arms and the deprotection of star polymers. For the synthesis ofarms, the molar ratio of reagents is: tBA/[(MMA)₂₀-co-(SMA)₇] (fromExample 1, Step 1)/EBiB/CuBr₂/Me₆TREN/V-70=160/0.2/0.8/0.01/0.05/0.025.Anisole (33%, v/v) was used as solvent. The synthesis of arms wasconducted as follows. In a 22 mL vial, CuBr₂ (33.3 mg) was dissolved inDMF (12 mL) with Me₆TREN (0.175 mL) to make a catalyst solution. An AceGlass reactor (1 L) was charged with [(MMA)₂₀-co-(SMA)₇] (13.3 g), tBA(350 mL), and anisole (155 mL). The DMF solution of CuBr₂/Me₆TREN (12mL) was added to the reactor. The resulting polymer solution was stirredfor 10 min in order to dissolve the macroinitiator, then the reactor wassealed with a rubber septum and the solution was purged with nitrogenfor 40 minutes. In a 100 mL round bottom flask was dissolved V-70 (115.5mg) in acetone (30 mL) and purged with N₂, and the resulting solutionwas transferred into a 60 mL syringe under N₂. The reactor was thenheated up to 65° C. and the acetone V-70 solution was fed into thereactor at the rate of 5 mL/h. The rate of addition was adjusted duringthe polymerization process in order to control the kinetics andexothermic effects of the reaction. Sample was taken for analysis and asthe conversion of monomer reached 42%, EBiB (1.75 mL) was then injected.The acetone V-70 solution was then fed at 5 mL/h rate. As the monomerconversion reached 83%, the reactor was opened to air. The cross-linkingof arms was continued in the same reactor with the molar ratio ofreagents as: [((MMA)₂₀-co-(SMA)₇)-b-(tBA)₁₆₉]/[(tBA)₆₆]arms_/DVB/CuBr₂/TPMA/Sn(EH)₂=1/20/0.012/0.072/0.14 in anisole. Asolution of CuBr₂/TPMA (36.2 mg CuBr₂/290 mg TPMA) in DMF (13.2 mL), DVB(39.4 mL), and anisole (200 mL) were added to the reactor, and theresulting polymer solution was purged with N₂ for 1 h. Then the reactorwas heated up to 95° C., and Sn(EH)₂ (0.63 mL) was injected to start thereaction. Sample was taken for analysis and 19 hours later as theconversion of DVB reached 64%, the heating was stopped and the reactorwas opened to air. Molecular weight of[(MMA)₂₀-co-(SMA)₇-b-(tBA)₁₆₉]/[(tBA)] star molecule was determined byGPC. Mn=49983 g/mol, Mp=108460 g/mol, PDI=2.49. The deprotection wasthen conducted by adding formic acid (150 mL) and sulfuric acid (0.3 mL)to the reactor. The reaction mixture was heated up to 75° C. After 6hours, the reaction was finished. The liquid was decanted and the solidpolymer was washed with acetonitrile and acetone in the flask for 3times. The solid polymer was recovered from the flask and dried invacuum oven at 40° C. for 1 day. Yield: the mass of[((MMA)₂₀-co-(SMA)₇)-b-(AA)₁₆₉]/[(AA)₆₆] star was 175 gram.

Example 3: Synthesis of[((MMA)₂₀-Co-(SMA)₇)-b-(AA)₆₉₈]/[(MMA)₁₅-b-(AA)₆₉₈]/[(AA)₉₈] Star (MolarRatio of Arms: 0.8/0.2/3, i.e., 4/1/15)

The “one-pot” procedure was used for the preparation of a poly(acrylicacid) based miktoarm star macromolecule similar to that described inScheme 1. The miktoarm star macromolecule with[((MMA)₂₀-co-(SMA)₇)-b-(AA)₆₉₈], [(MMA)₁₅-b-(AA)₆₉₈], and [(AA)₉₈] arms(molar ratio of arms: 0.8/0.2/3) was prepared as follows.

Step 1: Synthesis of a Poly(methyl methacrylate)-co-Poly(stearylmethacrylate) Macroinitiator [(MMA)₂₀-co-(SMA)₇] having 27 DP(#12-027-90) and Poly(methyl methacrylate) Macroinitiator [(MMA)₁₅]

Macroinitiator [(MMA)₂₀-co-(SMA)₇] was synthesized as described inExample 1, Step 1.

Macroinitiator [(MMA)₁₅] was synthesized by using Atom Transfer RadicalPolymerization (ATRP). The molar ratio of reagents is:MMA/DEBMM/CuBr/CuBr₂/bpy=22/1/0.2/0.02/0.44 in DMF (50% v/v). To a 500mL round bottom flask was added MMA (150 mL), DEBMM (12 m), CuBr₂ (0.31g), bpy (4.37 g), and DMF (150 mL), which was then sealed with a rubberseptum and the resulting solution was purged with nitrogen for 1 hour.Under nitrogen flow, the flask was opened and CuBr (1.8 g) was quicklyadded, the flask was then sealed and heated up to 50° C. After 2.5hours, the reaction was stopped, the polymer was precipitated withmethanol, and the molecular weight was measured by GPC. The Mn is 1525g/mol and PDI is 1.06. Yield: 80 grams of polymer was obtained afterpurification.

Steps 2-4: Synthesis of[((MMA)₂₀-Co-(SMA)₇)-b-(tBA)₆₉₈]/[(MMA)₁₅-b-(tBA)₆₉₈]/[(tBA)₉₈] Arms,Crosslinking and Deprotection to Produce[((MMA)₂₀-Co-(SMA)₇)-b-(AA)₆₉₈]/[(MMA)₁₅-b-(AA)₆₉₈]/[(AA)₉₈] StarCopolymer in “One Pot”

The synthesis includes 3 steps: the synthesis of arms, the cross-linkingof arms and the deprotection of star polymers. For the synthesis ofarms, the molar ratio of reagents is: tBA/[(MMA)₂₀-co-(SMA)₇] (fromExample 1, Step1)/[(MMA)₁₅]/EBiB/CuBr₂/Me₆TREN/V-70=200/0.2/0.05/0.75/0.0125/0.625/0.025.Anisole (33%, v/v) was used as solvent. The synthesis of arms wasconducted as follows. In a 22 mL vial, CuBr₂ (17.2 mg) was dissolved inDMF (5.94 mL) with Me₆TREN (0.1 mL) to make a stock solution. A 250 mLround bottom flask was charged with [(MMA)₂₀-co-(SMA)₇] (1.83 g),[(MMA)₁₅] (0.17 g), tBA (60 mL) and anisole (30 mL). The DMF solution ofCuBr₂/Me₆TREN (1.98 mL) was added to the flask, the resulting polymersolution was stirred for 10 min in order to dissolve the macroinitiator,the flask was sealed with a rubber septum, and the solution was purgedwith nitrogen for 40 minutes. In a 22 mL vial, V-70 (19.7 mg) wasdissolved in acetone (1 mL) and purged with N₂, and then transferredinto 1 mL syringe under N₂. The reaction flask was heated up to 65° C.,and then 0.1 mL of the V-70 actone solution was injected every 20minutes. Sample was taken for analysis and as the conversion of monomerreached 26%, EBiB (0.2 mL) was injected. After that, 0.1 mL of the V-70actone solution was injected every 30 minutes. As the monomer conversionreached 85%, the reaction flask was opened to air. The cross-linking ofarms was continued in the same flask with the molar ratio of reagentsas: [((MMA)₂₀-co-(SMA)₇)-b-(tBA)₆₉₈]/[(MMA)₁₅-b-(tBA)₆₉₈]/[(tBA)₉₈]arms/DVB/CuBr₂/TPMA/Sn(EH)₂=1/20/0.012/0.08/0.26 in anisole. A solutionof CuBr₂/TPMA (4.27 mg CuBr₂/40 mg TPMA) in DMF (2.4 mL), DVB (4.54 mL),and anisole (60 mL), were added to the flask. The polymer solution waspurged with N₂ for 1 h, then heated up to 95° C., and injected withSn(EH)₂ (0.08 mL), and the reaction started. Sample was taken foranalysis and 16 hours later as the conversion of DVB reached 64%, theheating was stopped and the flask was opened to air. Molecular weight of[((MMA)₂₀-co-(SMA)₇)-b-(tBA)₆₉₈]/[(MMA)₁₅-b-(tBA)₆₉₈]/[(tBA)₉₈] starmolecule was determined by GPC. Mn=92248 g/mol, Mp=167538 g/mol,PDI=2.38. The deprotection was then conducted by adding formic acid (20mL) and sulfuric acid (0.1 mL) to the flask. The reaction mixture washeated up to 75° C. After 6 hours, the reaction was finished. The liquidwas decanted and the solid polymer was washed with acetonitrile andacetone in the flask for 3 times. The solid polymer was recovered fromthe flask and dried in vacuum oven at 40° C. for 1 day. Yield: the massof [((MMA)₂₀-co-(SMA)₇)-b-(AA)₆₉₈]/[(MMA)₁₅-b-(AA)₆₉₈]/[(AA)₉₈] star was18 gram.

Example 4: Synthesis of [((MMA)₂₀-Co-(SMA)₇)-b-(AA)₄₆₁]/[(AA)₈₂] Star

The “one-pot” procedure was used for the preparation of a poly(acrylicacid) based miktoarm star macromolecule similar to that described inScheme 1. The miktoarm star macromolecule with[((MMA)₂₀-co-(SMA)₇)-b-(AA)₄₆₁] and [(AA)₈₂] arms (molar ratio of arms:1/4) was prepared as follows.

Step 1: Synthesis of a Poly(methyl methacrylate)-co-Poly(stearylmethacrylate) Macroinitiator [(MMA)₂₀-co-(SMA)₇]

Macroinitiator [(MMA)₂₀-co-(SMA)₇] was synthesized as described inExample 1, Step 1.

Steps 2-4: Synthesis of [((MMA)₂₀-Co-(SMA)₇)-b-(tBA)₄₆₁]/[(tBA)₈₂] Arms,Crosslinking and Deprotection to Produce[((MMA)₂₀-Co-(SMA)₇)-b-(AA)₄₆₁]/[(AA)₈₂] Star Copolymer in “One Pot”

The synthesis includes 3 steps: the synthesis of arms, the cross-linkingof arms and the deprotection of star polymers. For the synthesis ofarms, the molar ratio of reagents is: tBA/[(MMA)₂₀-co-(SMA)₇] (fromExample 1, Step1)/EBiB/CuBr₂/Me₆TREN/V-70=200/0.2/0.8/0.0125/0.0625/0.03. Anisole (26%,v/v) was used as solvent. The synthesis of arms was conducted asfollows. In a 22 mL vial, CuBr₂ (33.4 mg) was dissolved in DMF (12 mL)with Me₆TREN (0.20 mL) to make a catalyst solution. An Ace Glass reactor(1 L) was charged with [(MMA)₂₀-co-(SMA)₇] (10.99 g), tBA (350 mL), andanisole (120 mL). The DMF solution of CuBr₂/Me₆TREN (12 mL) was added tothe reactor, and the resulting polymer solution was stirred for 10 minin order to dissolve the macroinitiator. The reactor was sealed with arubber septum and the solution was purged with nitrogen for 40 minutes.In a 100 mL round bottom flask V-70 (115.5 mg) was dissolved in acetone(30 mL) and purged with N₂ and then transferred into 60 mL syringe underN₂. The 1 L reactor was then heated up to 65° C. and the acetonesolution of V-70 was fed at the rate of 5 mL/h. This rate was adjustedduring the polymerization process in order to control the kinetics andexothermic effects of the reaction. Sample was taken for analysis and asthe conversion of monomer reached 41%, EBiB (1.75 mL) was injected. Thenthe acetone solution of V-70 was fed at 5 mL/h rate. As the monomerconversion reached 82%, the flask was opened to air. The cross-linkingof arms was continued in the same flask with the molar ratio of reagentsas: [((MMA)₂₀-co-(SMA)₇)-b-(tBA)₄₆₁]/[(tBA)₈₂]arms/DVB/CuBr₂/TPMA/Sn(EH)₂=1/20/0.012/0.072/0.14 in anisole. A solutionof CuBr₂/TPMA (36.2 mg CuBr₂/330 mg TPMA) in DMF (13.2 mL), DVB (39.4mL), and anisole (600 mL), were added to the reactor, and the resultingpolymer solution was purged with N₂ for 1 h. The reactor was then heatedup to 95° C., and Sn(EH)₂ (1.05 mL) was injected, the reaction started.Sample was taken for analysis and 19 hours later as the conversion ofDVB reached 82%, the heating was stopped and the reactor was opened toair. Molecular weight of [((MMA)₂₀-co-(SMA)₇)-b-(tBA)₄₆₁]/[(tBA)₈₂] starmolecule was determined by GPC. Mn=94705 g/mol, Mp=254651 g/mol,PDI=2.87. The deprotection was then conducted by adding formic acid (150mL) and sulfuric acid (0.3 mL) to the reactor. The reaction mixture washeated up to 75° C. After 6 hours, the reaction was finished. The liquidwas decanted and the solid polymer was washed with acetonitrile andacetone in the reactor for 3 times. The solid polymer was recovered fromthe flask and dried in vacuum oven at 40° C. for 1 day. Yield: the massof [((MMA)₂₀-co-(SMA)₇)-b-(AA)₄₆₁]/[(AA)₈₂] star was 175 gram.

Properties of Star Copolymer (Examples 5-20)

The thickening property (influence on viscosity) and shear thinningproperty of aqueous solutions (water or surfactant-containing solutions)containing star macromolecules was investigated.

The viscosity of the aqueous solutions of the star macromolecules vs.shear rate was measured using a BROOKFIELD® LVDV-E Viscometer equippedwith a Spindle LVDVE SC4-31 at T=25° C. (shear rate=rpm×0.34), or if theviscosity it too great for that spindle, then a Spindle LVDVE SC4-25 atT=25° C. (shear rate=rpm×0.22). The viscosity of the samples weremeasured at 25° C., unless otherwise specified. In general, theviscosity ranges (cP) suitable for the Spindle LVDVE SC4-31 is 3 cP to100,000 cP, and the viscosity ranges (cP) suitable for the Spindle LVDVESC4-25 is 800 cP to 1,600,000 cP. For samples with viscosities withinthe test range having a viscosity below 100, Spindle SC4-31 should beselected.

Sample Preparation Procedure:

Aqueous gels at various concentrations (e.g., 0.2 wt. %, 0.25 wt %, 0.3wt. %, 0.4 wt. % 0.6 wt. %, 0.7 wt. % and 1.0 wt. %) of polymers wereprepared as follows: Deionized (DI) water (400 mL) was transferred to600 mL beaker, which was assembled below overhead stirrer IKA with mountstirring shaft with 3-blade marine impeller. The water was stirred at600 rpm to generate vortex, and to this was slowly sprinkled in acertain amount of the specified solid polymer. The resulting aqueouspolymer solution was then heated to 30° C., and if necessary, adjustedto a pH of 7 (e.g., add solid NaOH), and the stirring rate was thenincreased to 800 rpm, and then to 1600 rpm. The aqueous polymer solutionwas stirred for 15-20 min until the temperature reached 80-90° C. Theresulting mixture was then homogenized with a Silverson homogenizerequipped with a Square Hole workhead and Axial Flow workhead. Thehomogenizer stirring speed was gradually increased to 4800±200 rpm andmixed for 35 min. until a thick homogeneous gel was obtained. The pH ofthe resulting gel was analyzed with pH meter and, if necessary, adjustedto pH=7.0 (e.g., add solid NaOH).

Example 5: Thickening and Shear Thinning in Water

A gel from an aqueous solution containing 0.4 wt. % of a starmacromolecule (e.g., star macromolecule synthesized in Example 1, 2, 3or 4), was formed according to the Sample Preparation Procedure, using1.2 g of the specified solid polymer, 0.408 g solid NaOH, and the pH ofthe resulting gel was analyzed with pH meter and adjusted to pH=7.0.

The viscosity of the aqueous solution of the star macromolecule vs.shear rate was measured using the Spindle LVDVE SC4-25 at spindle ratesof 0.3, 0.5, 1.0, 2.0, 5.0, 10, 20, 30, 50, and 100 rpm. The results arepresented in FIGS. 2a and 2 b.

Example 6: SLES Surfactant Compatibility

A gel from an aqueous 6.4 wt. % SLES solution containing 2 wt. % of athickening agent (e.g., star macromolecule synthesized in Example 1,[(MMA)₁₅-b-(AA)₃₆₇]/[(AA)₈₂] star, [(St)₁₇-b-(AA)₄₅₄]/[(AA)₉₈] star, orCrothix Liquid), was formed according to the SLES SurfactantCompatibility Procedure:

For each sample, a 20 mL vial was charged with 25.5% active SLES aqueoussolution (5.0 g), thickening agent (0.4 g), NaOH (0.108 g; used only forExample 1, [(MMA)₁₅-b-(AA)₃₆₇]/[(AA)₈₂] star,[(St)₁₇-b-(AA)₄₅₄]/[(AA)₉₈] star, not for Crothix Liquid), and then acertain amount of deionized water to reach a total sample weight of 20g. The sample mixtures were then stirred at 70° C. for 2-4 hours untilall solids were dissolved, and then cooled at room temperature for 3hours.

The viscosity of the sample gels formed in the 6.4 wt. % SLES aqueoussystem vs. shear rate were measured (and comparator 6.4 wt. % SLESaqueous solution without any thickening agent): the sample containingExample 1 utilized Spindle LVDVE SC4-25, the samples containing[(MMA)₁₅-b-(AA)₃₆₇]/[(AA)₈₂] star, [(St)₁₇-b-(AA)₄₅₄]/[(AA)₉₈] star,Crothix Liquid, and SLES control, utilized Spindle LVDVE SC4-31, atspindle rates of 0.3, 0.5, 1.0, 2.0, 5.0, 10, 20, 30, 50, and 100 rpm.The results are presented in FIGS. 3a and 3 b.

Example 7

The influence of different thickening agent concentrations of starmacromolecule from Example 1 in 6.4 wt. % SLES aqueous system wasexamined using the SLES Surfactant Compatibility Procedure, using thefollowing specified amounts of thickening agent (0.3 g corresponded to1.5 wt. %, 0.4 g corresponded to 2.0 wt. %, or 0.5 g corresponded to 2.5wt. %), and NaOH (0.081 g for 1.5 wt. %, 0.108 g for 2 wt. %, or 0.135 gfor 2.5 wt. %).

The viscosity of the sample gels formed in the 6.4 wt. % SLES aqueoussystem were measured: the samples containing Example 1 at 0.0 wt. % and1.5 wt % utilized Spindle LVDVE SC4-31, and the samples containingExample 1 at 2.0 wt. % and 2.5 wt % utilized Spindle LVDVE SC4-25, atspindle rate of 1 rpm. The results are presented in FIG. 4.

Example 8

The influence of different surfactant SLES concentrations with 2 wt. %concentration of star macromolecule from Example 1 was examined usingthe SLES Surfactant Compatibility Procedure, using the followingspecified amounts of 25.5% active SLES aqueous solution (2.5 gcorresponded to 3.2 wt. %, 5.0 g corresponded to 6.4 wt. %, or 8.0 g for10.2 wt. %), thickening agent from Example 1 (0.4 g), and NaOH (0.081g).

The viscosity of the sample gels formed in the three differentconcentrations of SLES with 0.4 wt. % thickening agent from Example 1were measured using Spindle LVDVE SC4-25, at spindle rate of 1 rpm, andthe results are presented in FIG. 5.

Example 9: Shear Thinning in SLES Aqueous System

Four gels were prepared in a 6.4 wt. % SLES aqueous system (three gelswere formed using different amounts of star macromolecule from Example1, and one gel was formed using 2.5 wt. % of star macromolecule fromExample 2), using the SLES Surfactant Compatibility Procedure, using thefollowing specified amounts of thickening agent from Example 1 or 2 (0.3g corresponded to 1.5 wt. %, 0.4 g corresponded to 2.0 wt. %, or 0.5 gcorresponded to 2.5 wt. %), and NaOH (0.081 g for 1.5 wt. %, 0.108 g for2 wt. %, or 0.135 g for 2.5 wt. %).

The viscosity of the resulting sample gels formed in the 6.4 wt. % SLESaqueous system were measured: the samples containing Example 1 at 1.5wt. %, 2.0 wt. %, and 2.5 wt %, utilized Spindle LVDVE SC4-25, and thesamples containing Example 2 at 2.5 wt % and the SLES control, utilizedSpindle LVDVE SC4-31, at spindle rates of 0.3, 0.5, 1.0, 2.0, 5.0, 10,20, 30, 50, and 100 rpm. The results are presented in FIGS. 6a and 6 b.

Example 10: Temperature Stability

Gels were formed with 0.4 wt. % star macromolecules from Example 1-4according to the Sample Preparation Procedure, using 1.2 g of thespecified solid polymer, 0.408 g solid NaOH, and the pH of the resultinggel was analyzed with pH meter and adjusted to pH=7.0.

The viscosity of the aqueous solution of the star macromolecule wasmeasured using Spindle LVDVE SC4-25, at different temperatures(measurement taken after temperature of water bath and polymer solutionequilibrated for at least 15 min), at spindle rate of 1 rpm, and theresults are presented in FIG. 7.

Example 11: Hybrid SLES-CH Surfactant Compatibility

Gels from an aqueous 6.4 wt. % SLES/2.5 wt. % CocamidopropylHydroxysultaine (CH) solution containing 2 wt. % of a thickening agent(e.g., star macromolecules synthesized in Examples 1-3,[(St)₁₇-b-(AA)₄₅₄]/[(AA)₉₈] star, or Crothix Liquid), were formed usingthe Hybrid SLES-CH Surfactant Compatibility Procedure:

For each sample, a 20 mL vial was charged with 25.5% active SLES aqueoussolution (5.0 g), 50% active CH aqueous solution (1.0 g), thickeningagent (0.4 g), NaOH (0.108 g; used only for Examples 1-3 and[(St)₁₇-b-(AA)₄₅₄]/[(AA)₉₈] star, not for Crothix Liquid), and then acertain amount of deionized water to reach a total sample weight of 20g. The sample mixtures were then stirred at 70° C. for 2-4 hours untilall solids were dissolved, and then cooled at room temperature for 3hours.

The viscosity of the sample gels formed in the mixture 6.4 wt. %SLES/2.5 wt. % CH aqueous system vs. shear rate were measured (andcomparator mixture 6.4 wt. % SLES/2.5 wt. % CH aqueous system withoutany thickening agent): the samples containing Examples 1-3 and Crothixliquid utilized Spindle LVDVE SC4-25, and the samples containing[(St)₁₇-b-(AA)₄₅₄]/[(AA)₉₈] star and the SLES/CH control utilizedSpindle LVDVE SC4-31, at spindle rates of 0.3, 0.5, 1.0, 2.0, 5.0, 10,20, 30, 50, and 100 rpm. The results are presented in FIGS. 8a and 8 b.

Example 12

The influence of different thickening agent concentrations of starmacromolecule from Example 1 in 6.4 wt. % SLES/2.5 wt. % CH aqueoussystem was examined using the Hybrid SLES-CH Surfactant CompatibilityProcedure, using the following specified amounts of thickening agentfrom Example 1 (0.2 g corresponded to 1 wt. %, 0.3 g corresponded to 1.5wt. %, or 0.4 g corresponded to 2 wt. %), and NaOH (0.054 g for 1 wt. %,0.081 g for 1.5 wt. %, or 0.108 g for 2 wt. %).

The viscosity of the sample gels formed were measured: the samplescontaining Example 1 at 0.0 wt. % and 1.0 wt % utilized Spindle LVDVESC4-25, and the samples containing Example 1 at 1.5 wt. % and 2.0 wt %utilized Spindle LVDVE SC4-31, at spindle rate of 1 rpm. The results arepresented in FIG. 9.

Example 13

The influence of different surfactant SLES/CH concentrations with 2 wt.% concentration of star macromolecule from Example 1 was examined usingthe Hybrid SLES-CH Surfactant Compatibility Procedure, using thefollowing specified amounts of 25.5% active SLES aqueous solution (2.5 gcorresponded to 3.2 wt. %, 5.0 g corresponded to 6.4 wt. %, or 8.0 g for10.2 wt. %), 50% active CH aqueous solution (0.5 g of 1.3 wt. %, 1.0 gof 2.5 wt. %, or 1.6 g of 4.0 wt. %), thickening agent from Example 1(0.4 g), and NaOH (0.081 g).

The viscosity of the sample gels formed were measured using SpindleLVDVE SC4-25 at spindle rate of 1 rpm, and the results are presented inFIG. 10.

Example 14: Hybrid CB-SLES Surfactant Compatibility

Gels from an aqueous 6.4 wt. % Cocamidopropyl Betaine (CB)/2.5 wt. %SLES solution containing 1.5 wt. % of a thickening agent (e.g., starmacromolecules synthesized in Examples 1-2 or Crothix Liquid), wereformed using the Hybrid CB-SLES Surfactant Compatibility Procedure:

For each sample, a 20 mL vial was charged with 30% active CB aqueoussolution (4.27 g), 25.5% active SLES aqueous solution (1.96 g),thickening agent (0.3 g for Examples 1-2; or 0.66 g for Crothix Liquid),NaOH (0.082 g; used only for Examples 1-2, not for Crothix Liquid), andthen a certain amount of deionized water to reach a total sample weightof 20 g. The sample mixtures were then stirred at 70° C. for 2-4 hoursuntil all solids were dissolved, and then cooled at room temperature for3 hours.

The viscosity of the sample gels formed in the mixture 6.4 wt. % CB/2.5wt. % SLES aqueous system vs. shear rate were measured (and comparatormixture 6.4 wt. % CB/2.5 wt. % SLES aqueous system without anythickening agent): the samples containing Examples 1-2 utilized SpindleLVDVE SC4-25, and the samples containing Crothix liquid and the CB/SLEScontrol utilized Spindle LVDVE SC4-31, at spindle rates of 0.3, 0.5,1.0, 2.0, 5.0, 10, 20, 30, 50, and 100 rpm. The results are presented inFIGS. 11a and 11 b.

Example 15: Shear Thinning in Hybrid SLES/CH Aqueous System

Three gels were prepared in a hybrid 6.4 wt. % SLES/2.5 wt. % CH aqueoussystem (three gels were formed using different amounts of starmacromolecule from Example 1), using the Hybrid SLES/CH SurfactantCompatibility Procedure, using the following amounts of thickening agentfrom Example 1 (0.2 g for 1 wt. %, 0.3 g for 1.5 wt. %, or 0.4 g for 2wt. %), and NaOH (0.054 g for 1 wt. %, 0.081 g for 1.5 wt. %, or 0.108 gfor 2 wt. %). The viscosity vs. shear rate for each of the resultingsample gels formed was then examined.

The viscosity of the sample gels formed in the 6.4 wt. % SLES/2.5 wt. %CH aqueous system were measured: the samples containing Example 1 at 1.0wt. %, 1.5 wt. %, and 2.0 wt. %, utilized Spindle LVDVE SC4-25, and thesample containing the SLES/CH control utilized Spindle LVDVE SC4-31, atspindle rates of 0.3, 0.5, 1.0, 2.0, 5.0, 10, 20, 30, 50, and 100 rpm.The results are presented in FIGS. 12a and 12 b.

Example 16: pH Efficiency Range in Hybrid CB/SLES Aqueous System

Gels were formed in a hybrid 6.4 wt. % CB/2.5 wt. % SLES aqueous systemusing 1.5 wt. % star macromolecules from Examples 1-2 using the HybridCB-SLES Surfactant Compatibility Procedure. The pH of each solutionprepared was about 6. Each prepared solution was then cooled at roomtemperature for 3 hours.

The viscosity of the sample gels formed in the mixture 6.4 wt. % CB/2.5wt. % SLES aqueous system vs. shear rate were measured in accordance tothe Dynamic Viscosity Test Procedure at 1 rpm. This procedure wasrepeated for differing pH values, which was adjusted by the addition ofsodium hydroxide (or hydrochloric acid). The samples containing Example1 utilized Spindle LVDVE SC4-25, and the samples containing Example 2utilized Spindle LVDVE SC4-31. The results are presented in FIG. 13.

Example 17: pH Efficiency Range

An aqueous gel composition containing 0.4 wt. % of the starmacromolecule synthesized in Example 1 was prepared according to theprocedure of Example 5, in which the pH of the resulting gel wasanalyzed with pH meter and adjusted to pH=7.0.

The viscosity of the sample was measured using a Spindle LVDVE SC4-25,in accordance to the Dynamic Viscosity Test Procedure at 1 rpm. Thisprocedure was repeated for differing pH values, which was adjusted bythe addition of sodium hydroxide (or hydrochloric acid). The results arepresented in FIG. 14.

Example 18: Hybrid CB-SLES Surfactant with NaCl Compatibility

Gels from an aqueous 6.4 wt. % CB/2.5 wt. % SLES solution containing 1.5wt. % of a thickening agent (e.g., star macromolecules synthesized inExamples 1-2 or Crothix Liquid), were formed using the Hybrid CB-SLESSurfactant with NaCl Compatibility Procedure:

For each sample, a 20 mL vial was charged with 30% active CB aqueoussolution (4.27 g), 25.5% active SLES aqueous solution (1.96 g), acertain amount of thickening agent (0.3 g for Examples 1-2; 0.66 g forCrothix Liquid), NaOH (0.082 g; used only for Examples 1-2, not forCrothix Liquid), a certain amount of NaCl (1.0 g corresponded to 5 wt. %of salt, 2.0 g corresponded to 10 wt. % of salt), and then a certainamount of deionized water to reach a total sample weight of 20 g. Thesample mixtures were then stirred at 70° C. for 2-4 hours until allsolids were dissolved. The pH of each solution prepared was about 6.Each prepared solution was then cooled at room temperature for 3 hours.

The viscosity of the sample gels were measured in accordance to theDynamic Viscosity Test Procedure at 1 rpm. The samples containingExample 1, Example 2 (at 5 wt. % and 10 wt. % NaCl), and Crothix liquid(at 5 wt. % NaCl) utilized Spindle LVDVE SC4-25, and the samplescontaining Example 2 (at 0 wt. % NaCl), Crothix liquid (at 0 wt. % and10 wt. % NaCl), and CB/SLES control, utilized Spindle LVDVE SC4-31. Theresults are presented in FIG. 15.

Example 19

Surfactant compatibility test of a star macromolecule as thickeningagents in an aqueous system containing difficult-to-thicken surfactantsystems (e.g., 5 wt. % Ritabate 20; and 5 wt. % APG (C₈₋₁₆ fatty alcoholglycoside (PLANTAREN® 2000 N UP))).

Ritabate 20 Surfactant Compatibility:

A gel was formed with 2 wt. % of a thickening agent (e.g., starmacromolecule synthesized in Example 2) in an aqueous system containing5 wt. % Ritabate 20 and investigated using the Ritabate 20 SurfactantCompatibility Procedure:

For each sample, a 20 mL vial was charged with Ritabate 20 (1 g),thickening agent (0.4 g), NaOH (0.108 g), and then a certain amount ofdeionized water to reach a total sample weight of 20 g. The samplemixtures were then stirred at 70° C. for 2-4 hours until all solids weredissolved, cooled at room temperature for 3 hours, and then theviscosity of the gels in surfactant system vs. shear rate was examined.

APG Surfactant Compatibility:

A gel was formed with 2 wt. % of a thickening agent (e.g., starmacromolecule synthesized in Example 2) in an aqueous system containing5 wt. % APG (C₈₋₁₆ fatty alcohol glycoside (PLANTAREN® 2000 N UP)) andinvestigated using the APG Surfactant Compatibility Procedure:

For each sample, a 20 mL vial was charged with C₈₋₁₆ fatty alcoholglycoside (PLANTAREN® 2000 N UP; 50% active) (2 g), thickening agent(0.4 g), NaOH (0.108 g), and then a certain amount of deionized water toreach a total sample weight of 20 g. The sample mixtures were thenstirred at 70° C. for 2-4 hours until all solids were dissolved, cooledat room temperature for 3 hours, and then the viscosity of the gels insurfactant system vs. shear rate was examined.

The viscosity of the resulting sample gels was measured using a SpindleLVDVE SC4-25, and the results are presented in Table 2.

TABLE 2 2 wt. % Example 2 2 wt. % Example 2 Shear rate in 5 wt. %Ritabate 20 in 5 wt. % in APG [sec⁻¹] Viscosity [cP] Viscosity [cP]0.066 224000  11000 0.11 NA 8600 0.22 172300  5800 0.44 NA 4300 1.155100 3460 2.2 31200 3120 4.4 17020 3100 6.6 NA 2960 11  7594 2832 22 4728 2578

Example 20: Star Macromolecules as Thickening and Emulsifying Agents

The structure of the star macromolecules of the present invention, suchas the star macromolecule prepared in Example 1, may act not only asthickening agents but also as efficient emulsifying agents. Thephotographic image shown in FIG. 16 demonstrates the emulsifyingproperties of the star macromolecule of Example 1. The photographpresents water with 30 vol. % of sunflower oil (left vial) and waterwith 30 vol. % of sunflower oil and 0.3 wt. % of star macromolecule ofExample 1 (right vial). After vigorous mixing (as described in theEmulsion Test Procedure), phase separation occurred in the left vialwhile no phase separation was detected in the right vial upon visualinspection. The photograph of FIG. 16 was taken 2 days after theemulsion was prepared, indicating the thickening stability properties ofthe resulting gel.

Test Procedures:

Dynamic Viscosity Test Procedure

A portion of the gel prepared according to the Sample PreparationProcedure was transferred to the BROOKFIELD® LVDV-E Viscometer equippedwith a Spindle LVDVE SC4-31 (shear rate=rpm×0.34), or if the viscosityit too great for that spindle, then a Spindle LVDVE SC4-25 (shearrate=rpm×0.22), for mixing at 25° C. and at standard pressure (i.e., atSTP) over a wide range of rates (e.g, 0.3-100 rpm) and the shear rateand viscosity was recorded. Viscosity measurements were taken in thefollowing sequence, stopping the instrument after each measurement for 5minutes, 0.3, 0.5, 1, 2, 5, 10, 20, 30, 50, and 100 rpm. Dynamicviscosity was determined as the viscosity in centipoise (cP) at 1 rpm.

Shear-Thinning Value

A shear-thinning value was determined using values measured during theDynamic Viscosity Test Procedure, according to the following equation:

[(Viscosity(at 0.2 s⁻¹)−Viscosity(at 2.2 s⁻¹))/Viscosity(at 0.2s⁻¹)]×100%.

Thickening and Shear Thinning in Water Test

An aqueous solution of a macromolecule, when prepared according to theSample Preparation Procedure at a concentration of 0.4 wt. %, using aSpindle LVDVE SC4-25 for mixing at 25° C. and at standard pressure(i.e., at STP), forms a homogeneous gel at an adjusted pH of 7.0 and hasa Dynamic Viscosity of at least 5,000 cP at a shear rate of 2.2 s⁻¹ at25° C. and a Shear Thinning Value of at least 75%.

SLES Surfactant Compatibility Test

An aqueous solution of a macromolecule, when prepared according to theSLES Surfactant Compatibility Procedure at a concentration of 2.0 wt. %,using a Spindle LVDVE SC4-25 for mixing at 25° C. and at standardpressure (i.e., at STP), forms a homogeneous gel, the gel has a DynamicViscosity of at least 1,000 cP at a shear rate of 2.2 s⁻¹ at 25° C. andhas a Shear Thinning Value of at least 75%.

Hybrid SLES-CH Surfactant Compatibility Test

An aqueous solution of a macromolecule, when prepared according to theHybrid SLES-CH Surfactant Compatibility Procedure at a concentration of2.0 wt. %, using a Spindle LVDVE SC4-25 for mixing at 25° C. and atstandard pressure (i.e., at STP), forms a homogeneous gel, the gel has aDynamic Viscosity of at least 5,000 cP at a shear rate of 2.2 s⁻¹ at 25°C. and has a Shear Thinning Value of at least 35%.

Hybrid CB-SLES Surfactant Compatibility Test

An aqueous solution of a macromolecule, when prepared according to theHybrid CB-SLES Surfactant Compatibility Procedure at a concentration of1.5 wt. %, using a Spindle LVDVE SC4-25 for mixing at 25° C. and atstandard pressure (i.e., at STP), forms a homogeneous gel, the gel has aDynamic Viscosity of at least 2,000 cP at a shear rate of 2.2 s⁻¹ at 25°C. and has a Shear Thinning Value of at least 35%.

Hybrid CB-SLES Surfactant with NaCl Compatibility Test

An aqueous solution of a macromolecule, when prepared according to theHybrid CB-SLES Surfactant with NaCl Compatibility Procedure at aconcentration of 1.5 wt. %, and 5 wt. % NaCl, using a Spindle LVDVESC4-25 for mixing at 25° C. and at standard pressure (i.e., at STP),forms a homogeneous gel, the gel has a Dynamic Viscosity of at least5,000 cP at a shear rate of 0.22 s⁻¹ at 25° C.

Ritabate 20 Surfactant Compatibility Test

An aqueous solution of a macromolecule, when prepared according to theRitabate 20 Surfactant Compatibility Procedure at a concentration of 2.0wt. %, using a Spindle LVDVE SC4-25 for mixing at 25° C. and at standardpressure (i.e., at STP), forms a homogeneous gel, the gel has a DynamicViscosity of at least 15,000 cP at a shear rate of 2.2 s⁻¹ at 25° C.

APG Surfactant Compatibility Test

An aqueous solution of a macromolecule, when prepared according to theAPG Surfactant Compatibility Procedure at a concentration of 2.0 wt. %,using a Spindle LVDVE SC4-25 for mixing at 25° C. and at standardpressure (i.e., at STP), forms a homogeneous gel, the gel has a DynamicViscosity of at least 2,500 cP at a shear rate of 2.2 s⁻¹ at 25° C.

Temperature Stability Test

An aqueous solution of a macromolecule, when prepared according to theSample Preparation Procedure at a concentration of 0.4 wt. %, using aSpindle LVDVE SC4-25 for mixing at 25° C. and at standard pressure(i.e., at STP), forms a homogeneous gel at an adjusted pH of 7.0, has aDynamic Viscosity of at least 100,000 cP at a shear rate of 0.22 s⁻¹ at25° C., and has a Dynamic Viscosity at 80° C. that is at least 50%relative to the viscosity of the gel at 25° C. Temperature StabilityValues can be calculated using the following equation:

[Dynamic Viscosity(at 80° C.)/Dynamic Viscosity(at 25° C.)]×100%.

pH Efficiency Range in Hybrid CB/SLES Surfactant Test

An aqueous solution of a macromolecule, when prepared according to theHybrid CB-SLES Surfactant Compatibility Procedure at a concentration of1.5 wt. %, using a Spindle LVDVE SC4-25 for mixing at 25° C. and atstandard pressure (i.e., at STP), forms a homogeneous gel, the gel has aDynamic Viscosity of at least 8,000 cP at an adjusted pH in the range ofbetween 4.5 to 6.5 (e.g., by addition of NaOH or HCl), at a shear rateof 0.22 s⁻¹ at 25° C.

pH Efficiency Range Test

An aqueous solution of a macromolecule, when prepared according to theSample Preparation Procedure at a concentration of 0.4 wt. %, using aSpindle LVDVE SC4-25 for mixing at 25° C. and at standard pressure(i.e., at STP), forms a homogeneous gel, the gel has a Dynamic Viscosityof at least 5,000 cP at an adjusted pH in the range of between 5 to 12(e.g., by addition of NaOH or HCl), at a shear rate of 0.22 s⁻¹ at 25°C.

Hydrophilic-Lipophilic (HLB) Arm/Segment Calculation

HLB=20*Mh/M

where Mh is the molecular mass of the hydrophilic portion of thepolymeric arm or segment, and M is the molecular mass of the wholepolymeric arm or segment.

Hydrophilic-Lipophilic Macromolecule Calculation

${HLM} = {{\sum\limits_{n = 1}^{n = m}\; {{MW}_{n} \times {{HLB}_{n}/20}\mspace{14mu} {divided}\mspace{14mu} {by}\mspace{14mu} {0{.3}}\mspace{14mu} {MW}_{core}}} + {\sum\limits_{n = 1}^{n = m}\; {MW}_{n}}}$

where

MW_(n) is the molecular weight for the respective arm,HLB_(n) is the HLB, as calculated from the HLB arm calculation, for therespective arm, andMW_(core) is the molecular weight for the core, andM is the total number of arms.

1. A surfactant-system thickening macromolecule for increasing theviscosity of a surfactant-containing system, comprising: a) a core; b)at least one first polymeric arm, comprising a hydrophilic polymericsegment covalently attached to the core; and c) at least one secondpolymeric arm, comprising: i) a hydrophilic polymeric segment covalentlyattached to the core; and ii) a further segment covalently attached tothe hydrophilic polymeric segment, wherein the further segment iscomprised of at least one monomeric residue of a polymerizedsurfactant-system thickening monomer comprising a C₆ or greater alkylacrylate; C₆ or greater alkenyl acrylate; C₆ or greater alkyl alkylacrylate; C₆ or greater alkenyl alkyl acrylate; C₆ or greater alkylacrylamide; C₆ or greater alkenyl acrylamide; C₆ or greater alkyl alkylacrylamide; C₆ or greater alkenyl alkyl acrylamide; C₂ or greater alkylvinyl ether; C₂ or greater alkenyl vinyl ether; C₁ or greater alkylallyl ether; or C₁ or greater alkenyl allyl ether.
 2. The macromoleculeof claim 1, wherein the surfactant-system thickening macromolecule isrepresented by Formula A:[(P1)q1]r-Core-[(P3)_(q3)-(P2)_(q2)]_(s)  Formula A wherein: Corerepresents a crosslinked polymeric segment; P1 independently representsthe hydrophilic polymeric segment of the at least first polymeric armcomprised of monomeric residues of polymerized hydrophilic monomers; P2independently represents the further segment of the at least secondpolymeric arm comprised of at least one monomeric residue of apolymerized surfactant-system thickening monomer; P3 independentlyrepresents the hydrophilic polymeric segment of the at least secondpolymeric arm comprised of monomeric residues of polymerized hydrophilicmonomers; q1 independently represents the number of monomeric residuesin P1; q2 independently represents the number of monomeric residues inP2; q3 independently represents the number of monomeric residues in P3;r independently represents the number of the at least first polymericarms covalently attached to the Core; and s independently represents thenumber of the at least second polymeric arms covalently attached to theCore.
 3. The macromolecule of claim 1, wherein the surfactant-systemthickening macromolecule is represented by Formula B:

wherein: Core represents a crosslinked polymeric segment; P1independently represents the hydrophilic polymeric segment of the atleast first polymeric arm comprised of monomeric residues of polymerizedhydrophilic monomers; P2 independently represents the further segment ofthe at least second polymeric arm comprised of at least one monomericresidue of a polymerized surfactant-system thickening monomer; P3independently represents the hydrophilic polymeric segment of the atleast second polymeric arm comprised of monomeric residues ofpolymerized hydrophilic monomers; P4 independently represents thehydrophobic polymeric segment of the at least third polymeric armcomprised of monomeric residues of polymerized hydrophobic monomers; P5independently represents the hydrophilic polymeric segment of the atleast third polymeric arm comprised of monomeric residues of polymerizedhydrophilic monomers; q1 independently represents the number ofmonomeric residues in P1; q2 independently represents the number ofmonomeric residues in P2; q3 independently represents the number ofmonomeric residues in P3; q4 independently represents the number ofmonomeric residues in P4; q5 independently represents the number ofmonomeric residues in P5; r independently represents the number of theat least first polymeric arms covalently attached to the Core; sindependently represents the number of the at least second polymericarms covalently attached to the Core; and t independently represents thenumber of the at least third polymeric arms covalently attached to theCore.
 4. The macromolecule of claim 3, wherein a portion of the furthersegment is represented by Formula E:

wherein: R¹¹, R¹², R¹³ independently represent hydrogen, methyl, ethyl,or C₃₋₁₈ alkyl; wherein the alkyl may be branched or unbranched, linearor cyclic, and may be optionally substituted with one or more halogens,C₁₋₆ alkoxy groups, or poly(ethylene glycol); R¹⁴ independentlyrepresents C₁₋₁₂ hydrocarbyl, —C₁₋₁₂ hydrocarbyl-(O—C₁₋₆hydrocarbyl)_(w), —C₁₋₁₂ hydrocarbyl-((CO)O—C₁₋₆ hydrocarbyl)_(w),—C₁₋₁₂ hydrocarbyl-((CO)NH—C₁₋₆ hydrocarbyl)_(w); wherein eachhydrocarbyl portion independently may be branched or unbranched, linearor cyclic, saturated (alkyl) or unsaturated (alkenyl), and may beoptionally substituted with one or more halogens, C₁₋₆ alkoxy groups, orpoly(ethylene glycol); R¹⁵ independently represents C₁₃₋₄₀ hydrocarbyl,—C₁₃₋₄₀ hydrocarbyl-(O—C₁₋₆ hydrocarbyl)_(w), —C₁₃₋₄₀hydrocarbyl-((CO)O—C₁₋₆ hydrocarbyl)_(w), C₁₃₋₄₀hydrocarbyl-((CO)NH—C₁₋₆ alkyl)_(w); wherein each hydrocarbyl portionindependently may be branched or unbranched, linear or cyclic, saturated(alkyl) or unsaturated (alkenyl), and may be optionally substituted withone or more halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol); or ahydrophobic moiety of a surfactant, a hydrophobic moiety of a lipid, ora hydrophobic moiety of a fatty alcohol; Y represents a covalent bond,ethylene glycol, poly(ethylene glycol), polyether, polyamide, C₁₋₆alkyl, or combinations thereof, or is independently absent; mindependently represents a value in the range of 1-500; n independentlyrepresents a value in the range of 1-500; and w independently representsa value in the range of 1-1000.
 5. The macromolecule of claim 1, whereinthe surfactant-system thickening macromolecule has a molecular weight(Mn) in the range of between 5,000 g/mol and 10,000,000 g/mol.
 6. Themacromolecule of claim 1, wherein the molecular weight (Mn) of the atleast one polymeric arm is between 1,000 g/mol to 250,000 g/mol.
 7. Themacromolecule of claim 1, wherein when 0.4 wt. % of the macromoleculeforms a homogeneous gel, the gel has a dynamic viscosity of at least100,000 cP at a shear rate of 0.22 s⁻¹ at 25° C., and has a DynamicViscosity at 80° C. that is at least 50% relative to the viscosity ofthe gel at 25° C., according to the Temperature Stability Test.
 8. Themacromolecule of claim 1, wherein when 1.5 wt. % of the macromoleculeforms a homogeneous gel, the gel has a dynamic viscosity of at least8,000 cP at an adjusted pH in the range of between 4.5 to 6.5 at a shearrate of 0.22 s⁻¹ at 25° C., according to the pH Efficiency Range inHybrid CB/SLES Surfactant Test.
 9. The macromolecule of claim 1, whereinwhen 0.4 wt. % of the macromolecule forms a homogeneous gel, the gel hasa dynamic viscosity of at least 5,000 cP at an adjusted pH in the rangeof between 5 to 12 at a shear rate of 0.22 s⁻¹ at 25° C., according tothe pH Efficiency Range Test.
 10. A surfactant-modified starmacromolecule, comprising: i) a core; ii) at least one first polymericarm, comprising a hydrophilic polymeric segment covalently attached tothe core; and iii) at least one second polymeric arm, comprising: a) ahydrophilic polymeric segment covalently attached to the core; and b) afurther segment comprising at least one pendant moiety represented by[L¹-G¹-L²-G²];  wherein: G1 independently represents a residue of ahydrophilic moiety of the surfactant; G2 independently represents aresidue of a hydrophobic moiety of the surfactant; L1 independentlyrepresents a linking group or a covalent bond, attaching G1 to thefurther segment; and L2 independently represents a linking group or acovalent bond, linking G1 and G2.
 11. A method of increasing theviscosity of a surfactant-containing aqueous system, comprising:introducing the surfactant-system thickening macromolecule of-claim 1into the surfactant-containing aqueous system.
 12. A method ofincreasing the viscosity of a surfactant-containing aqueous system,comprising: introducing the surfactant-modified star macromolecule ofclaim 10 into the surfactant-containing aqueous system.
 13. A method ofincreasing the viscosity of a surfactant-containing aqueous system,comprising: introducing a surfactant-system thickening macromoleculeinto the surfactant-containing aqueous system, wherein thesurfactant-system thickening macromolecule comprises: i) a core; ii) atleast one first polymeric arm, comprising a polymeric segment comprisedof monomeric residues of polymerized hydrophilic monomers; and iii) atleast one second polymeric arm, comprises: 1) at least one pendantmicelle-philic moiety; or 2) a polymeric segment comprised of at leastone monomeric residue of a polymerized micelle-philic monomer.
 14. Themethod of claim 13, wherein the at least one pendant micelle-philicmoiety is represented by the formula:[L¹-G¹-L²-G²] wherein: G¹ independently represents a residue of ahydrophilic moiety of the surfactant; G² independently represents aresidue of a hydrophobic moiety of the surfactant; L¹ independentlyrepresents a linking group or a covalent bond, attaching G¹ to the atleast one second polymeric arm; and L² independently represents alinking group or a covalent bond, linking G¹ and G².
 15. The method ofclaim 13, wherein the at least one pendant micelle-philic moiety or theat least one monomeric residue of a polymerized micelle-philic monomercomprises a C6 or greater alkyl moiety, a fluorine-modified C4 orgreater alkyl moiety, or a C6 or greater alkenyl moiety.
 16. The methodof claim 13, wherein the at least one pendant micelle-philic moiety orthe at least one monomeric residue of a polymerized micelle-philicmonomer comprises the hydrophobic moiety of a commercially suitablesurfactant and/or registered in TSCA.
 17. The method of claim 13,wherein the micelle-philic monomer is represented by Formula I-V:

wherein: R¹, R², and R³ independently represent hydrogen, methyl, ethyl,or C₃₋₁₈ alkyl; wherein the alkyl may be branched or unbranched, linearor cyclic, and may be optionally substituted with one or more halogens,C₁₋₆ alkoxy groups, or poly(ethylene glycol); R⁴ and R⁷ independentlyrepresent C₁₃ or greater alkyl, —C₆ or greater alkyl-(O—C₁₋₆ alkyl)_(n),C₆ or greater alkenyl, or C₆ or greater alkenyl-(O—C₁₋₆ alkyl)_(n); orwhen R³ is C₁ or greater, then R⁴ may independently represent C₁₁ orgreater alkyl, —C₆ or greater alkyl —(O—C₁₋₆ alkyl)_(n), C₆ or greateralkenyl, or C₆ or greater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkylportion independently may be branched or unbranched, linear or cyclic,saturated or unsaturated, and may be optionally substituted with one ormore halogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol); R⁵independently represents C₁₉ or greater alkyl, —C₆ or greater alkyl—(O—C₁₋₆ alkyl)_(n), C₆ or greater alkenyl, or C₆ or greateralkenyl-(O—C₁₋₆ alkyl)_(n); or when R⁶ is C₁ or greater, then R⁵ mayindependently represent C₁₃ or greater alkyl, —C₆ or greater alkyl—(O—C₁₋₆ alkyl)_(n), C₆ or greater alkenyl, or C₆ or greateralkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkyl portion independently maybe branched or unbranched, linear or cyclic, saturated or unsaturated,and may be optionally substituted with one or more halogens, C₁₋₆ alkoxygroups, or poly(ethylene glycol); R⁶ independently represents hydrogen,C₁₋₁₈ alkyl, —C₁₋₁₈ alkyl-(O—C₁₋₆ alkyl)_(n), or is R⁴, or is R⁵;wherein each alkyl portion independently may be branched or unbranched,linear or cyclic, saturated or unsaturated, and may be optionallysubstituted with one or more halogens, C₁₋₆ alkoxy groups, orpoly(ethylene glycol); R⁸ independently represents C₂ or greater alkyl,—C₂ or greater alkyl-(O—C₁₋₆ alkyl)_(n), C₃ or greater alkenyl, —C₃ orgreater alkenyl-(O—C₁₋₆ alkyl)_(n); wherein each alkyl portionindependently may be branched or unbranched, linear or cyclic, saturatedor unsaturated, and may be optionally substituted with one or morehalogens, C₁₋₆ alkoxy groups, or poly(ethylene glycol); R⁹ independentlyrepresents C₁ or greater alkyl, —C₁ or greater alkyl-(O—C₁₋₆ alkyl)_(n),C₃ or greater alkenyl, —C₃ or greater alkenyl-(O—C₁₋₆ alkyl)_(n);wherein each alkyl portion independently may be branched or unbranched,linear or cyclic, saturated or unsaturated, and may be optionallysubstituted with one or more halogens, C₁₋₆ alkoxy groups, orpoly(ethylene glycol); or R⁴, R⁵, R⁷, R⁸, R⁹ independently represent ahydrophobic portion of a surfactant, a hydrophobic portion of a lipid,or a hydrophobic portion of a fatty alcohol; A¹, A², A³ and A⁴independently represent CH, CR¹⁰, or N, wherein at least two of A¹, A²,A³ and A⁴ is CH or CR¹⁰; R¹⁰ independently represents hydrogen, C₁₋₁₀alkyl, halogen, hydroxyl, C₁₋₁₀ alkoxy; wherein the alkyl or alkoxy maybe branched or unbranched, linear or cyclic, and may be optionallysubstituted with one or more halogens, C₁₋₆ alkoxy groups, orpoly(ethylene glycol); Y independently represents a covalent bond, —O—,—S—, —N(H)—, —N(R¹)—, —(CO)—, —S(O)—, —S(O)₂—, —S(O)₂N(R¹)—,—(CO)N(R¹)—, —N(R¹)—(CO)—, —(CO)O—, or —O—(CO)—; L¹ independentlyrepresents a covalent bond, ethylene glycol, poly(ethylene glycol),polyether, polyamide, C₁₋₆ alkyl, —(CO)N(R¹)—, —N(R¹)—(CO)—, —(CO)O—,—O—(CO)—, or combinations thereof, or is independently absent; or L¹independently represents a hydrophilic portion of a surfactant, ahydrophilic portion of a lipid, or a hydrophilic portion of a fattyalcohol; L² independently represents (CH₂)₁₋₄₀, C₁₋₄₀ alkyl, (O—C₂₋₆alkyl)_(n), or (C₂₋₆ alkyl)-(O—C₂₋₆ alkyl)_(n); wherein the alkyl may bebranched or unbranched, linear or cyclic, and may be optionallysubstituted with one or more halogens, C₁₋₆ alkoxy groups, orpoly(ethylene glycol); and n independently represents a value in therange of 1-1000.
 18. The method of claim 13, wherein the surfactant is anonionic surfactant, an anionic surfactant, an amphoteric surfactant, ora cationic surfactant.